TW201627415A - Coloring composition, color filter, pattern forming method, method for producing color filter, solid-state imagine element and image display device - Google Patents

Coloring composition, color filter, pattern forming method, method for producing color filter, solid-state imagine element and image display device Download PDF

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TW201627415A
TW201627415A TW104139535A TW104139535A TW201627415A TW 201627415 A TW201627415 A TW 201627415A TW 104139535 A TW104139535 A TW 104139535A TW 104139535 A TW104139535 A TW 104139535A TW 201627415 A TW201627415 A TW 201627415A
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group
dye
compound
formula
color filter
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TWI712655B (en
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Yousuke Murakami
Yoshinori Taguchi
Junichi Itou
Hiroaki Idei
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices

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  • Physics & Mathematics (AREA)
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  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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  • Materials For Photolithography (AREA)
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Abstract

A coloring composition which contains a dye A having a triarylmethane skeleton, a dye B having a xanthene skeleton and a curable compound, and wherein at least one of the dye A and the dye B is a dye multimer; a color filter which uses this coloring composition; a pattern forming method; a method for producing a color filter; a solid-state imaging element; and an image display device.

Description

著色組成物、彩色濾光片、圖案形成方法、彩色濾光片的製造方法、固體攝像元件以及圖像顯示装置Coloring composition, color filter, pattern forming method, method of manufacturing color filter, solid-state imaging element, and image display device

本發明係有關一種著色組成物。又，係有關一種彩色濾光片、圖案形成方法、彩色濾光片的製造方法、固體攝像元件以及圖像顯示装置。The present invention relates to a colored composition. Further, the present invention relates to a color filter, a pattern forming method, a method of manufacturing a color filter, a solid-state image sensor, and an image display device.

作為具備CCD或CMOS等圖像感測器之固體攝像元件、液晶顯示装置以及其他光學元件的核心設備，使用彩色濾光片。彩色濾光片通常具備紅（R）、綠（G）以及藍（B）這3原色的著色圖案，發揮將透射光分解為3原色之作用。A color filter is used as a core device including a solid-state imaging element such as a CCD or a CMOS image sensor, a liquid crystal display device, and other optical elements. The color filter usually has a color pattern of three primary colors of red (R), green (G), and blue (B), and functions to decompose transmitted light into three primary colors.

將著色組成物應用於玻璃基板等基材上，進行100℃左右的預烘烤，接著形成已進行曝光以及顯影之圖案，進行210℃左右的後烘烤，藉此製造出彩色濾光片。The colored composition is applied to a substrate such as a glass substrate, prebaked at about 100 ° C, and then patterned to be exposed and developed, and post-baked at about 210 ° C to produce a color filter.

一直以來，使用含有彩色指數（C.I.）顏料藍15:6和C.I.顏料紫23之著色組成物製造藍色的著色圖案（藍色的彩色濾光片）。 專利文献1中公開有使用含有具有呫噸骨架之色素多聚物和C.I.顏料藍15:6之著色組成物來製造彩色濾光片。 又，專利文献2中公開有使用含有具有三芳基甲烷骨架之色素多聚物之著色組成物來製造彩色濾光片。 【先前技術文獻】 【專利文獻】A blue coloring pattern (blue color filter) has been produced using a coloring composition containing color index (C.I.) Pigment Blue 15:6 and C.I. Pigment Violet 23. Patent Document 1 discloses the production of a color filter using a coloring composition containing a dye polymer having a xanthene skeleton and C.I. Pigment Blue 15:6. Further, Patent Document 2 discloses that a color filter is produced using a coloring composition containing a dye multipolymer having a triarylmethane skeleton. [Prior Art Literature] [Patent Literature]

【專利文獻1】日本特開2012-32754號公報 【專利文獻2】美國專利申請公開第2013/0141810號說明書[Patent Document 1] JP-A-2012-32754 (Patent Document 2) US Patent Application Publication No. 2013/0141810

專利文献1中公開之彩色濾光片的分光特性比以往的藍色彩色濾光片、亦即使用含有由C.I.顏料藍15:6和C.I.顏料紫23的組合構成之著色劑之著色組成物形成之彩色濾光片的分光特性優異，但近幾年要求進一步提高彩色濾光片的分光特性。 另一方面，就三芳基甲烷單獨來說，具有分光特性差之傾向，了解到專利文献2中公開之彩色濾光片的分光特性差。The color filter of the color filter disclosed in Patent Document 1 is formed of a coloring composition of a conventional blue color filter, that is, a coloring agent containing a coloring agent composed of a combination of CI Pigment Blue 15:6 and CI Pigment Violet 23 The color filter has excellent spectral characteristics, but in recent years, it is required to further improve the spectral characteristics of the color filter. On the other hand, the triarylmethane alone has a tendency to have poor spectral characteristics, and the spectral characteristics of the color filter disclosed in Patent Document 2 are poor.

近幾年，進行液晶顯示装置的發光光源的有機電致發光（有機EL）化以及圖像感測器的光電轉換膜的有機材料化。在其特性上，要求在100℃左右的低溫下製造彩色濾光片。 然而，了解到在低溫下硬化而製造之彩色濾光片具有耐溶劑性下降之傾向。In recent years, organic electroluminescence (organic EL) of an illuminating light source of a liquid crystal display device and organic materialization of a photoelectric conversion film of an image sensor have been performed. In terms of its characteristics, it is required to manufacture a color filter at a low temperature of about 100 °C. However, it is understood that a color filter manufactured by hardening at a low temperature has a tendency to have a decrease in solvent resistance.

藉此，本發明的目的為提供一種能夠形成分光特性以及耐溶劑性良好之彩色濾光片等硬化膜之著色組成物、彩色濾光片、圖案形成方法、彩色濾光片的製造方法、固體攝像元件以及圖像顯示装置。Accordingly, an object of the present invention is to provide a colored composition of a cured film such as a color filter excellent in spectral characteristics and solvent resistance, a color filter, a pattern forming method, a method of producing a color filter, and a solid. Imaging element and image display device.

本發明人等經過詳細的研究之結果，發現藉由倂用具有呫噸骨架之色素和具有三芳基甲烷骨架之色素，能夠形成分光特性良好之硬化膜。而且，發現即使在將選自具有呫噸骨架之色素以及具有三芳基甲烷骨架之色素之至少一種作為色素多聚物，藉此在低溫下將著色組成物硬化而形成硬化膜的情況下，亦可獲得耐溶劑性優異之硬化膜，並完成了本發明。本發明提供以下。 ＜1＞一種著色組成物，其含有：具有三芳基甲烷骨架之色素A；具有呫噸骨架之色素B；以及硬化性化合物，選自色素A以及色素B之至少一種為色素多聚物。 ＜2＞如＜1＞所述之著色組成物，其中色素A以及色素B為色素多聚物。 ＜3＞如＜1＞所述之著色組成物，其中色素A的三芳基甲烷骨架的莫耳數與色素B的呫噸骨架的莫耳數之比為40:60～75:25｡ ＜4＞如＜1＞～＜3＞中任一項所述之著色組成物，其中選自色素A以及色素B之至少一種具有選自雙（磺醯基）亞胺陰離子、三（磺醯基）甲基化物陰離子（tris(sulfonyl)methide anion）以及四芳基硼酸鹽陰離子之至少一種陰離子。 ＜5＞如＜1＞～＜4＞中任一項所述之著色組成物，其中色素A含有具有三芳基甲烷骨架之陽離子部和經由共價鍵與陽離子部鍵結之陰離子。 ＜6＞如＜1＞～＜4＞中任一項所述之著色組成物，其中色素B含有具有呫噸骨架之陽離子部和經由共價鍵與陽離子部鍵結之陰離子。 ＜7＞如＜1＞～＜6＞中任一項所述之著色組成物，其中選自色素A以及色素B之至少一種具有含有聚合性不飽和雙鍵之基團。 ＜8＞一種彩色濾光片，其使用＜1＞～＜7＞中任一項所述之著色組成物。 ＜9＞如＜8＞所述之彩色濾光片，其用於有機電致發光元件。 ＜10＞一種圖案形成方法，其包括： 使用＜1＞～＜7＞中任一項所述之著色組成物，在支撐體上形成著色組成物層之製程； 將著色組成物層曝光成圖案狀之製程； 對未曝光部進行顯影去除而形成著色圖案之製程；以及 在50～120℃下對著色圖案進行加熱之製程。 ＜11＞一種彩色濾光片的製造方法，其包括＜10＞所述之圖案形成方法。 ＜12＞一種固體攝像元件，其具有＜8＞所述之彩色濾光片。 ＜13＞一種圖像顯示装置，其具有＜8＞所述之彩色濾光片。As a result of detailed studies, the present inventors have found that a cured film having good spectral characteristics can be formed by using a dye having a xanthene skeleton and a dye having a triarylmethane skeleton. Further, it has been found that even when at least one selected from the group consisting of a dye having a xanthene skeleton and a dye having a triarylmethane skeleton is used as a dye polymer, whereby the colored composition is cured at a low temperature to form a cured film, A cured film excellent in solvent resistance can be obtained, and the present invention has been completed. The present invention provides the following. <1> A coloring composition comprising: a dye A having a triarylmethane skeleton; a dye B having a xanthene skeleton; and a curable compound selected from at least one of the dye A and the dye B as a dye polymer. <2> The colored composition according to <1>, wherein the dye A and the dye B are dye polymers. <3> The coloring composition according to <1>, wherein the ratio of the molar number of the triarylmethane skeleton of the dye A to the molar number of the xanthene skeleton of the dye B is 40:60 to 75:25. <4 The coloring composition according to any one of <1> to <3> wherein at least one selected from the group consisting of the dye A and the dye B has an anion selected from the group consisting of bis(sulfonyl)imide anion and tris(sulfonyl) At least one anion of a tris(sulfonyl)methide anion and a tetraarylborate anion. The colored composition according to any one of <1> to <4> wherein the dye A contains a cation portion having a triarylmethane skeleton and an anion bonded to the cation portion via a covalent bond. The colored composition according to any one of <1> to <4> wherein the dye B contains a cation portion having a xanthene skeleton and an anion bonded to the cation portion via a covalent bond. The colored composition according to any one of <1> to <6> wherein at least one selected from the group consisting of the dye A and the dye B has a group containing a polymerizable unsaturated double bond. <8> A color filter using the coloring composition according to any one of <1> to <7>. <9> A color filter according to <8>, which is used for an organic electroluminescence element. <10> A pattern forming method, comprising: a process of forming a colored composition layer on a support by using the colored composition according to any one of <1> to <7>; exposing the colored composition layer to a pattern Process for forming a colored pattern by developing and removing the unexposed portion; and heating the colored pattern at 50 to 120 ° C. <11> A method of producing a color filter, comprising the pattern forming method according to <10>. <12> A solid-state image sensor having the color filter of <8>. <13> An image display device comprising the color filter of <8>.

依本發明，可以提供能夠形成分光特性以及耐溶劑性良好之彩色濾光片等硬化膜之著色組成物、彩色濾光片、圖案形成方法、彩色濾光片的製造方法、固體攝像元件以及圖像顯示装置。According to the present invention, it is possible to provide a colored composition of a cured film such as a color filter excellent in spectral characteristics and solvent resistance, a color filter, a pattern forming method, a method of producing a color filter, a solid-state image sensor, and a figure. Like a display device.

以下，對本發明的內容進行詳細說明。 在本說明書中之基團（原子團）的標記中，未標註取代以及無取代之標記係，包含不具有取代基者，而且包含具有取代基者。例如“烷基”係指不僅包含不具有取代基之烷基（無取代烷基），而且亦包含具有取代基之烷基（取代烷基）者。 在本說明書中，光係指活性光線或放射線。又，“活性光線”或“放射線”係指例如水銀燈的明線光譜、準分子雷射所代表之遠紫外線、極紫外線（EUV光）、X射線、電子束等。 在本說明書中的“曝光”，只要沒有特別的指明，則不僅指水銀燈、準分子雷射所代表之遠紫外線、X射線、EUV光等之曝光，基於電子束、離子束等粒子束之描畫亦包含於曝光中。 在本說明書中，由“～”表示之數值範圍係指將“～”的前後所記載之數值作為下限值以及上限值而包括在內之範圍。 在本說明書中，總固體成分係指從著色組成物的總體組成中去除溶劑之後的成分的總質量。 在本說明書中，“（甲基）丙烯酸酯”表示丙烯酸酯以及丙烯酸甲酯兩者或任一者，“（甲基）丙烯酸”表示丙烯酸以及甲基丙烯酸兩者或任一者，“（甲基）烯丙基”表示烯丙基以及甲基烯丙基兩者或任一者，“（甲基）丙烯醯基”表示丙烯醯基以及甲基丙烯醯基兩者或任一者。 在本說明書中，聚合性化合物係指具有聚合性官能基之化合物，可以為單體，亦可為聚合物。聚合性官能基係指參與聚合反應之基團。 在本說明書中，化學式中的Me表示甲基，Et表示乙基，Pr表示丙基，Bu表示丁基，Ph表示苯基。 在本說明書中，“製程”這一術語不僅包括獨立製程，而且即使在無法與其他製程明確地區別的情況下，只要能夠實現該製程的所期待的作用，則亦包含於本術語中。 在本說明書中，重量平均分子量以及數量平均分子量被定義為藉由凝膠滲透色譜法（GPC）測定而獲得之聚苯乙烯換算値。Hereinafter, the contents of the present invention will be described in detail. In the labeling of the group (atomic group) in the present specification, a labeling system which does not have a substitution or an unsubstituted group, and which has no substituent, and which has a substituent. For example, "alkyl" means an alkyl group (substituted alkyl group) having not a substituent but also an alkyl group having a substituent (substituted alkyl group). In the present specification, light refers to active light or radiation. Further, "active light" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, or the like. The "exposure" in this specification refers to not only the exposure of far-ultraviolet light, X-ray, EUV light, etc. represented by mercury lamps and excimer lasers, but also the drawing of particle beams based on electron beams, ion beams, etc., unless otherwise specified. Also included in the exposure. In the present specification, the numerical range represented by "to" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present specification, the total solid content means the total mass of the components after removing the solvent from the overall composition of the coloring composition. In the present specification, "(meth) acrylate" means either or both of acrylate and methyl acrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid, "(A) The "allyl" group means either or both of an allyl group and a methallyl group, and "(meth)acryloyl group" means either or both of an acryloyl group and a methacryl group. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in the polymerization reaction. In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the term "process" includes not only independent processes, but also the term as long as it can achieve the desired effect of the process, even if it is not clearly distinguishable from other processes. In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-converted oximes obtained by gel permeation chromatography (GPC).

＜著色組成物＞ 本發明的著色組成物含有：具有三芳基甲烷骨架之色素A；具有呫噸骨架之色素B；以及硬化性化合物，選自色素A以及色素B之至少一種為色素多聚物。 藉由將本發明的著色組成物設成上述結構，能夠形成分光特性以及耐溶劑性良好之彩色濾光片等硬化膜。亦即，藉由倂用具有三芳基甲烷骨架之色素和具有呫噸骨架之色素，能夠形成分光特性良好之硬化膜。而且，藉由將選自具有三芳基甲烷骨架之色素以及具有呫噸骨架之色素之至少一種設為色素多聚物，即使在低溫下將著色組成物硬化而形成硬化膜的情況下，亦可獲得耐溶劑性優異之硬化膜。又，色素不易從膜上脫落，還能夠抑制與其他顏色之間的混色。 又，本發明的著色組成物的上述色素A以及上述色素B為色素多聚物為較佳。具有三芳基甲烷骨架之色素和具有呫噸骨架之色素的相溶性良好，很難形成締合狀態。故，抑制色素之間的相分離，能夠抑制溶劑的滲入等，可獲得優異之耐溶劑性。又，藉由將兩者設為色素多聚物，色素更加不易從膜上脫落，能夠有效地抑制與其他顏色之間的混色。 又，本發明的著色組成物的上述色素A的三芳基甲烷骨架的莫耳數與上述色素B的呫噸骨架的莫耳數之比為40:60～75:25為較佳。只要兩者之比為上述範圍，便能夠更加提高硬化膜的耐溶劑性。又，能夠更加有效地抑制與其他顏色之間的混色。又，能夠抑制發生膜成分的滲出（bleed out）等，膜的可靠性優異。 又，本發明的著色組成物的選自上述色素A以及上述色素B之至少一種具有選自雙（磺醯基）亞胺陰離子、三（磺醯基）甲基化物陰離子以及四芳基硼酸鹽陰離子之陰離子為較佳。與氯型陰離子等相比，上述陰離子不易發生鹽交換，能夠形成耐熱性優異之硬化膜。又，能夠抑制發生膜成分的滲出等，膜的可靠性優異。 以下，對本發明進行詳細說明。<Coloring composition> The coloring composition of the present invention contains: a dye A having a triarylmethane skeleton; a dye B having a xanthene skeleton; and a curable compound selected from at least one of the dye A and the dye B as a dye polymer . By setting the coloring composition of the present invention to the above configuration, it is possible to form a cured film such as a color filter having excellent spectral characteristics and solvent resistance. In other words, by using a dye having a triarylmethane skeleton and a dye having a xanthene skeleton, a cured film having good spectral characteristics can be formed. In addition, when at least one selected from the group consisting of a dye having a triarylmethane skeleton and a dye having a xanthene skeleton is used as a dye polymer, even when the colored composition is cured at a low temperature to form a cured film, A cured film excellent in solvent resistance is obtained. Further, the pigment is less likely to fall off from the film, and color mixing with other colors can be suppressed. Further, the dye A and the dye B of the colored composition of the present invention are preferably a dye polymer. The dye having a triarylmethane skeleton and the pigment having a xanthene skeleton have good compatibility, and it is difficult to form an association state. Therefore, phase separation between the dyes is suppressed, and penetration of a solvent or the like can be suppressed, and excellent solvent resistance can be obtained. Further, by using both of them as the dye polymer, the dye is less likely to fall off from the film, and color mixing with other colors can be effectively suppressed. Further, the coloring composition of the coloring composition of the present invention preferably has a molar ratio of the number of moles of the triarylmethane skeleton of the dye A to the number of moles of the xanthene skeleton of the dye B of 40:60 to 75:25. As long as the ratio of the two is within the above range, the solvent resistance of the cured film can be further improved. Moreover, color mixing with other colors can be more effectively suppressed. Moreover, it is possible to suppress the occurrence of bleeding of the film component, and the like, and the reliability of the film is excellent. Further, at least one selected from the above-mentioned dye A and the above dye B of the coloring composition of the present invention has a selected from the group consisting of bis(sulfonyl)imide anion, tris(sulfonyl)methide anion, and tetraarylborate. An anion anion is preferred. The anion is less likely to undergo salt exchange than a chlorine anion or the like, and a cured film excellent in heat resistance can be formed. Moreover, it is possible to suppress the occurrence of bleeding of the film component or the like, and the reliability of the film is excellent. Hereinafter, the present invention will be described in detail.

＜＜著色劑＞＞ 本發明的著色組成物含有具有三芳基甲烷骨架之色素A和具有呫噸甲烷骨架之色素B作為著色劑。在本發明中，選自色素A以及色素B之至少一種為色素多聚物，色素A以及色素B均為色素多聚物為較佳。 另外，在本發明中，色素多聚物係指，在一分子中具有2個以上的三芳基甲烷骨架或呫噸骨架之化合物。<<Colorant>> The coloring composition of the present invention contains a dye A having a triarylmethane skeleton and a dye B having a xanthene methane skeleton as a colorant. In the present invention, at least one selected from the group consisting of the dye A and the dye B is a dye multimer, and both the dye A and the dye B are preferably a dye polymer. Further, in the present invention, the dye multimer refers to a compound having two or more triarylmethane skeletons or xanthene skeletons in one molecule.

在本發明中，色素A含有具有三芳基甲烷骨架之陽離子部和陰離子為較佳。又，色素B含有具有呫噸骨架之陽離子部和陰離子為較佳。 在本發明中，可以在陽離子部的分子外具有陰離子，但經由共價鍵與陽離子部鍵結為較佳。另外，在陽離子部的分子外具有陰離子係指，陽離子部與陰離子不經由共價鍵鍵結，而是作為分體的化合物存在之情況。以下，將陽離子部的分子外的陰離子亦稱作對陰離子。 在本發明中，色素A實質上不含有呫噸骨架為較佳。又，色素B實質上不含有三芳基甲烷骨架為較佳。In the present invention, the dye A preferably contains a cation portion having an triarylmethane skeleton and an anion. Further, the dye B preferably contains a cation portion and an anion having a xanthene skeleton. In the present invention, an anion may be provided outside the molecule of the cation portion, but it is preferably bonded to the cation portion via a covalent bond. Further, an anionic moiety is present outside the molecule of the cation moiety, and the cation moiety and the anion are not bonded via a covalent bond, but are present as a compound of a split. Hereinafter, the extra-molecular anion of the cation portion is also referred to as a counter anion. In the present invention, it is preferred that the dye A does not substantially contain a xanthene skeleton. Further, it is preferred that the dye B does not substantially contain a triarylmethane skeleton.

在本發明中，色素A在著色組成物中的含量為著色組成物的總固體成分的5～60質量%為較佳。上限為55質量%以下為更佳，50質量%以下為進一步較佳。下限為10質量%以上為更佳，15質量%以上為進一步較佳。 在本發明中，色素B在著色組成物中的含量為著色組成物的總固體成分的5～60質量%為較佳。上限為55質量%以下為更佳，50質量%以下為進一步較佳。下限為7.5質量%以上為更佳，10質量%以上為進一步較佳。 在本發明中，色素A和色素B在著色劑總量中的總量為50～100質量%為較佳。下限為65質量%以上為更佳，70質量%以上為進一步較佳。 在本發明中，色素A的三芳基甲烷骨架的莫耳數與色素B的呫噸骨架的莫耳數之比為40:60～75:25為較佳，45:55～65:35為更佳。只要兩者之比為上述範圍，便能夠更加提高硬化膜的耐溶劑性。又，能夠更加有效地抑制與其他顏色之間的混色。又，能夠抑制發生膜成分的滲出等，膜的可靠性優異。 另外，在本發明中，在色素A為單量體的情況下，色素A的三芳基甲烷骨架的莫耳數指的是色素A的莫耳數。又，在色素A為色素多聚物的情況下，指的是除了三芳基甲烷骨架以外的部分之部位（例如，後述通式（A）的DyeI、後述通式（C）的DyeIII、後述通式（D-1）的D）的莫耳數。關於色素B的呫噸骨架的莫耳數亦相同。In the present invention, the content of the dye A in the colored composition is preferably from 5 to 60% by mass based on the total solid content of the colored composition. The upper limit is preferably 55% by mass or less, more preferably 50% by mass or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. In the present invention, the content of the dye B in the colored composition is preferably from 5 to 60% by mass based on the total solid content of the colored composition. The upper limit is preferably 55% by mass or less, more preferably 50% by mass or less. The lower limit is preferably 7.5 mass% or more, and more preferably 10 mass% or more. In the present invention, the total amount of the dye A and the dye B in the total amount of the colorant is preferably from 50 to 100% by mass. The lower limit is preferably 65 mass% or more, and more preferably 70 mass% or more. In the present invention, the ratio of the molar number of the triarylmethane skeleton of the dye A to the molar number of the xanthene skeleton of the dye B is preferably 40:60 to 75:25, and more preferably 45:55 to 65:35. good. As long as the ratio of the two is within the above range, the solvent resistance of the cured film can be further improved. Moreover, color mixing with other colors can be more effectively suppressed. Moreover, it is possible to suppress the occurrence of bleeding of the film component or the like, and the reliability of the film is excellent. Further, in the present invention, when the dye A is a single body, the molar number of the triarylmethane skeleton of the dye A refers to the number of moles of the dye A. In addition, when the dye A is a dye polymer, it means a part other than the triarylmethane skeleton (for example, DyeI of the following general formula (A), DyeIII of the following general formula (C), and the following. The number of moles of D) of the formula (D-1). The molar number of the xanthene skeleton of the pigment B is also the same.

在本發明中，選自色素A以及色素B之至少一種含有具有聚合性不飽和雙鍵之基團（以下，亦簡稱為“聚合性基”）為較佳，兩者含有聚合性基為更佳。藉由設成該種結構，具有耐溶劑性更加提高之傾向。又，更加不易產生與其他顏色之間的混色。又，能夠抑制發生膜成分的滲出等。 在1分子中含有2個以上聚合性基為較佳。作為聚合性基，可以舉出乙烯基、（甲基）烯丙基以及（甲基）丙烯醯基，（甲基）丙烯醯基為較佳。In the present invention, at least one selected from the group consisting of the dye A and the dye B preferably contains a group having a polymerizable unsaturated double bond (hereinafter also referred to simply as "polymerizable group"), and both of them contain a polymerizable group. good. By providing such a structure, solvent resistance tends to be improved. Moreover, it is more difficult to produce a color mixture with other colors. Further, it is possible to suppress the occurrence of bleeding of the film component or the like. It is preferred to contain two or more polymerizable groups in one molecule. Examples of the polymerizable group include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group, and a (meth) acrylonitrile group is preferred.

＜＜＜具有三芳基甲烷骨架之色素A＞＞＞ 在本發明中，作為具有三芳基甲烷骨架之色素A，可例示由下述式（TP）表示之結構。<<<Pigment A having a triarylmethane skeleton>>> In the present invention, the dye A having a triarylmethane skeleton is represented by the following formula (TP).

式（TP） 【化學式1】 Formula (TP) [Chemical Formula 1]

式（TP）中，Rtp1 ～Rtp4 分別獨立地表示氫原子、烷基或芳基。Rtp5 表示氫原子、烷基、芳基或NRtp9 Rtp10 （Rtp9 以及Rtp10 表示氫原子、烷基或芳基）。Rtp6 、Rtp7 以及Rtp8 表示取代基。a、b以及c表示0～4的整數。在a、b以及c為2以上的情況下，Rtp6 、Rtp7 以及Rtp8 亦可分別連結而形成環。X- 表示陰離子結構。在不存在X- 的情況下，Rtp1 ～Rtp7 的至少1個含有陰離子。In the formula (TP), Rtp 1 to Rtp 4 each independently represent a hydrogen atom, an alkyl group or an aryl group. Rtp 5 represents a hydrogen atom, an alkyl group, an aryl group or NRtp 9 Rtp 10 (Rtp 9 and Rtp 10 represent a hydrogen atom, an alkyl group or an aryl group). Rtp 6 , Rtp 7 and Rtp 8 represent a substituent. a, b, and c represent integers of 0-4. When a, b, and c are 2 or more, Rtp 6 , Rtp 7 , and Rtp 8 may be bonded to each other to form a ring. X - represents an anionic structure. In the absence of X - , at least one of Rtp 1 to Rtp 7 contains an anion.

在色素A為色素多聚物的情況下，經由式（TP）中的Rtp1 ～Rtp10 的任1個與色素多聚物的其他部位（後述通式（A）的L1 或後述通式（1）的R2 為較佳）鍵結為較佳，經由Rtp5 與色素多聚物的其他部位鍵結為更佳。When the dye A is a dye polymer, it is passed through any one of Rtp 1 to Rtp 10 in the formula (TP) and another portion of the dye polymer (L 1 of the general formula (A) or a later formula It is preferred that the R 2 of (1) is preferred, and it is preferably bonded to other sites of the dye polymer via Rtp 5 .

作為Rtp1 ～Rtp6 ，氫原子、碳原子數1～5的直鏈或支鏈的烷基以及苯基為較佳。Rtp5 為氫原子或NRtp9 Rtp10 為較佳，NRtp9 Rtp10 為特佳。Rtp9 以及Rtp10 為氫原子、碳原子數1～5的直鏈或者支鏈的烷基或苯基為較佳。Rtp6 、Rtp7 以及Rtp8 所表示之取代基可以舉出日本特開2014-237809號公報的段落號0042～0053中記載之取代基組A，但碳原子數1～5的直鏈或者支鏈的烷基、碳原子數1～5的烯基、碳原子數6～15的芳基、羧基或磺酸基為特佳，碳原子數1～5的直鏈或者支鏈的烷基、碳原子數1～5的烯基、苯基或羧基為進一步較佳。Rtp6 、Rtp8 為碳原子數1～5的烷基為特佳，Rtp7 為烯基（尤其是相鄰之2個烯基所連結之苯基為較佳）、苯基或羧基為較佳。 a、b或c分別獨立地表示0～4的整數。a以及c分別為0或1為特佳，0為更佳。b為0～2的整數為較佳，0或2為更佳。Rtp 1 to Rtp 6 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group. Rtp 5 is preferably a hydrogen atom or NRtp 9 Rtp 10 , and NRtp 9 Rtp 10 is particularly preferred. Rtp 9 and Rtp 10 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms or a phenyl group. The substituent represented by Rtp 6 , Rtp 7 and Rtp 8 may be a substituent group A described in paragraphs 0942 to 0053 of JP-A-2014-237809, but a linear or branched carbon number of 1 to 5. An alkyl group of the chain, an alkenyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a carboxyl group or a sulfonic acid group, particularly preferably a linear or branched alkyl group having 1 to 5 carbon atoms; An alkenyl group, a phenyl group or a carboxyl group having 1 to 5 carbon atoms is further preferred. Rtp 6 and Rtp 8 are particularly preferably an alkyl group having 1 to 5 carbon atoms, Rtp 7 is an alkenyl group (especially a phenyl group in which two adjacent alkenyl groups are bonded), and a phenyl group or a carboxyl group is preferred. good. a, b or c each independently represents an integer of 0-4. It is particularly preferable that a and c are 0 or 1 respectively, and 0 is more preferable. An integer of b is preferably 0 to 2, and 0 or 2 is more preferable.

在Rtp1 ～Rtp7 的至少1個含有陰離子的情況下，作為陰離子，-SO3 - 、-COO- 、-PO4 - 、雙（磺醯基）亞胺陰離子、三（磺醯基）甲基化物陰離子以及四芳基硼酸鹽陰離子為較佳，雙（磺醯基）亞胺陰離子、三（磺醯基）甲基化物陰離子以及四芳基硼酸鹽陰離子為更佳，雙（磺醯基）亞胺陰離子以及三（磺醯基）甲基化物陰離子為進一步較佳。 具體而言，可以舉出Rtp1 ～Rtp7 的至少1個被通式（P）取代之結構。 通式（P） 【化學式2】通式（P）中，L表示單鍵或2價連結基，X1 表示陰離子。When at least one of Rtp 1 to Rtp 7 contains an anion, as an anion, -SO 3 - , -COO - , -PO 4 - , bis(sulfonyl)imide anion, tris(sulfonyl) A A carboxylate anion and a tetraarylborate anion are preferred, and a bis(sulfonyl)imide anion, a tris(sulfonyl)methide anion, and a tetraarylborate anion are more preferred, bis(sulfonyl) The imine anion and the tris(sulfonyl)methide anion are further preferred. Specifically, at least one of Rtp 1 to Rtp 7 may be substituted by the formula (P). General formula (P) [Chemical Formula 2] In the formula (P), L represents a single bond or a divalent linking group, and X 1 represents an anion.

通式（P）中，L表示單鍵或2價連結基。作為2價連結基，表示-NR10 -、-O-、-SO2 -、亦可含有取代基（例如可以舉出鹵素原子、羥基，氟原子為較佳）之伸烷基、亦可含有取代基（例如可以舉出鹵素原子、羥基，氟原子為較佳）之伸芳基或由該些組合構成之基團為較佳。由-NR10 -、-SO2 以及含有氟原子之伸烷基的組合構成之基團、由-O-和含有氟原子之伸芳基的組合構成之基團或由-NR10 -、-SO2 以及含有氟原子之伸烷基的組合構成之基團為特佳。 在-NR10 -中，R10 表示氫原子或碳原子數1～5的烷基，氫原子為較佳。 伸烷基的碳原子數為1～10為較佳，1～6為更佳，1～3為進一步較佳。作為含有氟原子之伸烷基，全氟伸烷基為更佳。作為含有氟原子之伸烷基的具體例，可以舉出二氟亞甲基、四氟乙烯基、六氟丙烯等。 伸芳基的碳原子數為6～20為較佳，6～14為更佳，6～10為進一步較佳。作為含有氟原子之伸芳基的具體例，可以舉出四氟伸苯基、六氟-1-亞萘基、六氟-2-伸萘基等。In the formula (P), L represents a single bond or a divalent linking group. Examples of the divalent linking group include -NR 10 -, -O-, -SO 2 -, and an alkyl group which may further contain a substituent (for example, a halogen atom, a hydroxyl group, or a fluorine atom), and may also contain A substituent group (for example, a halogen atom, a hydroxyl group, or a fluorine atom is preferred) or a group composed of the combinations is preferred. a group consisting of a combination of -NR 10 -, -SO 2 and a stretching alkyl group containing a fluorine atom, a group consisting of a combination of -O- and a fluorine-containing extended aryl group or by -NR 10 -, - A group composed of a combination of SO 2 and an alkyl group having a fluorine atom is particularly preferable. In -NR 10 -, R 10 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom is preferred. The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. As the alkylene group having a fluorine atom, a perfluoroalkylene group is more preferable. Specific examples of the alkylene group containing a fluorine atom include difluoromethylene, tetrafluoroethylene, and hexafluoropropylene. The number of carbon atoms of the aryl group is preferably from 6 to 20, more preferably from 6 to 14, and further preferably from 6 to 10. Specific examples of the extended aryl group containing a fluorine atom include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group, and a hexafluoro-2-naphthyl group.

通式（P）中，X1 表示陰離子，選自-SO3 - 、-COO- 、-PO4 - 、雙（磺醯基）亞胺陰離子、三（磺醯基）甲基化物陰離子以及四芳基硼酸鹽陰離子之1種為較佳，選自雙（磺醯基）亞胺陰離子、三（磺醯基）甲基化物陰離子以及四芳基硼酸鹽陰離子之1種為更佳，雙（磺醯基）亞胺陰離子或三（磺醯基）甲基化物陰離子為進一步較佳。In the formula (P), X 1 represents an anion selected from the group consisting of -SO 3 - , -COO - , -PO 4 - , bis(sulfonyl)imide anion, tris(sulfonyl)methide anion, and tetra One of the aryl borate anions is preferred, and one selected from the group consisting of bis(sulfonyl)imide anion, tris(sulfonyl)methide anion, and tetraarylborate anion is more preferred, double ( A sulfonyl)imide anion or a tris(sulfonyl)methide anion is further preferred.

在Rtp1 ～Rtp7 的至少1個含有陰離子的情況下，Rtp1 ～Rtp7 的至少1個被通式（P-1）取代之結構亦較佳。 通式（P-1） 【化學式3】通式（P-1）中，L1 表示單鍵或2價連結基，單鍵為較佳。作為L1 所表示之2價連結基，可以舉出碳原子數1～6的伸烷基、碳原子數6～12的伸芳基、-O-、-S-或由該些組合構成之基團等。 L2 表示-SO2 -或-CO-。 G表示碳原子或氮原子。 G為碳原子時，n1表示2，G為氮原子時，n1表示1。 R6 表示含有氟原子之烷基或含有氟原子之芳基。n1為2時，2個R6 可以相同，亦可不同。 R6 所表示之含有氟原子之烷基的碳原子數為1～10為較佳，1～6為更佳，1～3為進一步較佳。 R6 所表示之含有氟原子之芳基的碳原子數為6～20為較佳，6～14為更佳，6～10為進一步較佳。When at least one of Rtp 1 to Rtp 7 contains an anion, at least one of Rtp 1 to Rtp 7 is preferably substituted with the formula (P-1). General formula (P-1) [Chemical Formula 3] In the formula (P-1), L 1 represents a single bond or a divalent linking group, and a single bond is preferred. Examples of the divalent linking group represented by L 1 include an alkylene group having 1 to 6 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, -O-, and -S- or a combination thereof. Group and so on. L 2 represents -SO 2 - or -CO-. G represents a carbon atom or a nitrogen atom. When G is a carbon atom, n1 represents 2, and when G is a nitrogen atom, n1 represents 1. R 6 represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. When n1 is 2, two R 6 's may be the same or different. The alkyl group having a fluorine atom represented by R 6 has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. The aryl group containing a fluorine atom represented by R 6 has preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and further preferably 6 to 10 carbon atoms.

另外，在色素A中，陽離子如下非定域化地存在。 【化學式4】 Further, in the dye A, the cation exists as follows in a non-localized manner. [Chemical Formula 4]

＜＜＜具有呫噸骨架之色素B＞＞＞ 在本發明中，作為具有呫噸骨架之色素B，可例示由下述式（J）表示之結構。<<<Pigment B having a xanthene skeleton>>> In the present invention, the dye B having a xanthene skeleton is exemplified by the following formula (J).

【化學式5】 [Chemical Formula 5]

式（J）中，R81 、R82 、R83 以及R84 分別獨立地表示氫原子或1價取代基，R85 分別獨立地表示1價取代基，m表示0～5的整數。X- 表示對陰離子。在不存在X- 的情況下，R81 ～R85 的至少1個含有陰離子。In the formula (J), R 81 , R 82 , R 83 and R 84 each independently represent a hydrogen atom or a monovalent substituent, and R 85 each independently represents a monovalent substituent, and m represents an integer of 0 to 5. X - represents a pair of anions. In the absence of X - , at least one of R 81 to R 85 contains an anion.

在色素B為色素多聚物的情況下，經由式（J）中R81 ～R85 的任1個與色素多聚物的其他部位（後述通式（A）的L1 或後述通式（1）的R2 為較佳）鍵結為較佳，經由R85 與色素多聚物的其他部位鍵結為更佳。When the dye B is a dye polymer, it is passed through any one of R 81 to R 85 in the formula (J) and another portion of the dye polymer (L 1 of the general formula (A) or a formula (hereinafter described) It is preferred that the R 2 of 1) is preferably bonded, and it is preferably bonded to other sites of the dye polymer via R 85 .

式（J）中的R81 ～R85 所能取之取代基可以舉出日本特開2014-237809號公報的段落號0042～0053中記載之取代基組A，該內容編入本說明書中。 式（J）中的R81 以及R82 、R83 以及R84 以及m為2以上時的R85 之間亦可分別獨立地相互鍵結而形成5員、6員或者7員飽和環或5員、6員或者7員的不飽和環。作為所形成之環，例如可以舉出吡咯環、呋喃環、噻吩環、吡唑環、咪唑環、***環、噁唑環、噻唑環、吡咯烷環、哌啶環、環戊烯環、環己烯環、苯環、吡啶環、吡嗪環、噠嗪環，可較佳地舉出苯環、吡啶環。 所形成之環還為可取代之基團的情況下，可以由以R81 ～R85 説明之取代基取代，在由2個以上的取代基取代的情況下，該些取代基可以相同，亦可不同。The substituent group which can be obtained by R 81 to R 85 in the formula (J) is the substituent group A described in paragraphs 0942 to 0053 of JP-A-2014-237809, which is incorporated herein by reference. In formula (J) R 81 and R 82, R 83 and R 84 and m may each independently be bonded to each other between the 2 or more R 85 to form a 5, 6 or 7-membered saturated ring or a 5 Unsaturated ring of 6 members or 7 members. Examples of the ring to be formed include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, and a cyclopentene ring. The cyclohexene ring, the benzene ring, the pyridine ring, the pyrazine ring, and the pyridazine ring are preferably a benzene ring or a pyridine ring. When the ring to be formed is also a substitutable group, it may be substituted by a substituent described by R 81 to R 85 , and when substituted by two or more substituents, the substituents may be the same, Can be different.

式（J）中，R82 以及R83 為氫原子或取代或無取代的烷基，R81 以及R84 為取代或無取代的烷基或苯基為較佳。又，R85 為鹵素原子、碳原子數1～5的直鏈或支鏈的烷基、磺酸基、磺醯胺基、羧基、醯胺基為較佳，磺酸基、磺醯胺基、羧基、醯胺基為進一步較佳。R85 鍵結於與呫噸環連結之碳的相鄰部為較佳。R81 以及R84 的苯基所具有之取代基為氫原子、鹵素原子、碳原子數1～5的直鏈或支鏈的烷基、磺酸基、磺醯胺基、羧基為特佳。In the formula (J), R 82 and R 83 are a hydrogen atom or a substituted or unsubstituted alkyl group, and R 81 and R 84 are a substituted or unsubstituted alkyl group or a phenyl group. Further, R 85 is a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfonic acid group, a sulfonylamino group, a carboxyl group or a decylamino group, and a sulfonic acid group or a sulfonylamino group. Further, a carboxyl group or a guanamine group is further preferred. R 85 is preferably bonded to an adjacent portion of the carbon to which the xanthene ring is bonded. The substituent of the phenyl group of R 81 and R 84 is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfonic acid group, a sulfonylamino group or a carboxyl group.

在R81 ～R85 的至少1個含有陰離子的情況下，作為陰離子可以舉出上述陰離子。When at least one of R 81 to R 85 contains an anion, the anion may be mentioned as an anion.

由式（J）表示之具有呫噸骨架之化合物能夠利用文献記載之方法合成。具體而言，能夠應用四面體快報（Tetrahedron Letters）、2003年、vol.44、No.23、4355～4360頁、四面體、2005年、vol.61、No.12、3097～3106頁等中記載之方法。The compound having a xanthene skeleton represented by the formula (J) can be synthesized by a method described in the literature. Specifically, it is possible to apply Tetrahedron Letters, 2003, vol. 44, No. 23, 4355 to 4360 pages, tetrahedron, 2005, vol. 61, No. 12, 3097 to 3106, and the like. The method of recording.

在X- 表示陰離子的情況下，能夠參閱後述之對陰離子為其他分子的情況的記載。 又，在不存在X- 且R81 、R82 、R83 以及R84 的至少1個含有陰離子的情況下，能夠參閱對陰離子位於同一結構單元内之情況的記載。When X - represents an anion, the description of the case where the anion is another molecule will be described later. Further, in the case where X - is absent and at least one of R 81 , R 82 , R 83 and R 84 contains an anion, the description of the case where the anion is located in the same structural unit can be referred to.

另外，色素B中，陽離子如下非定域化地存在。 【化學式6】 Further, in the dye B, the cation is present in a non-localized manner as follows. [Chemical Formula 6]

＜＜＜對陰離子＞＞＞ 在本發明中，在色素A和/或色素B由陽離子部和對陰離子構成的情況下，作為對陰離子無特別限制，但從耐熱性的觀點考慮，非親核性的陰離子為較佳。作為非親核性的陰離子，日本特開2007-310315號公報的段落號0075等中記載之公知的非親核性陰離子為較佳。在此，非親核性係指，不會因加熱而對色素進行親核攻擊之性質。 作為對陰離子，選自磺酸陰離子、羧酸陰離子、磺醯亞胺陰離子、雙（磺醯基）亞胺陰離子、三（磺醯基）甲基化物陰離子、羧酸陰離子、四芳基硼酸陰離子、-CON- CO-、-CON- SO2 -、BF4 - 、PF6 - 、SbF6 - 、B- （CN）3 OCH3 之至少一種為較佳。選自雙（磺醯基）亞胺陰離子、三（磺醯基）甲基化物陰離子以及四芳基硼酸鹽陰離子之至少一種為更佳，選自雙（磺醯基）亞胺陰離子以及三（磺醯基）甲基化物陰離子之至少一種為進一步較佳。 對陰離子為具有由下述（AN-1）～（AN-5）表示之結構之非親核性陰離子為更佳。<<<Poly anion>>> In the present invention, when the dye A and/or the dye B are composed of a cationic portion and a counter anion, the anion is not particularly limited, but from the viewpoint of heat resistance, non-nucleophilic Sex anions are preferred. As the non-nucleophilic anion, a known non-nucleophilic anion described in Paragraph No. 0075 of JP-A-2007-310315 or the like is preferred. Here, non-nucleophilic means a property that does not cause nucleophilic attack on a pigment by heating. As a counter anion, selected from the group consisting of a sulfonate anion, a carboxylate anion, a sulfonimide anion, a bis(sulfonyl)imide anion, a tris(sulfonyl)methide anion, a carboxylate anion, a tetraarylborate anion , -CON - CO -, - CON - SO 2 -, BF 4 -, PF 6 -, SbF 6 -, B - (CN) 3 OCH 3 at least one of the preferred. More preferably, at least one selected from the group consisting of a bis(sulfonyl)imide anion, a tris(sulfonyl)methide anion, and a tetraarylborate anion is selected from the group consisting of bis(sulfonyl)imide anions and three ( At least one of the sulfonyl) methide anions is further preferred. It is more preferable that the anion is a non-nucleophilic anion having a structure represented by the following (AN-1) to (AN-5).

【化學式7】 [Chemical Formula 7]

式（AN-1）中，X1 以及X2 分別獨立地表示氟原子或具有氟原子之碳原子數1～10的烷基。X1 以及X2 可以相互鍵結而形成環。 X1 以及X2 分別獨立地表示氟原子或具有氟原子之碳原子數1～10的烷基，氟原子或具有氟原子之碳原子數1～10的烷基為較佳，碳原子數1～10的全氟烷基為更佳，碳原子數1～4的全氟烷基為進一步較佳，三氟甲基為特佳。In the formula (AN-1), X 1 and X 2 each independently represent a fluorine atom or an alkyl group having a fluorine atom and having 1 to 10 carbon atoms. X 1 and X 2 may be bonded to each other to form a ring. X 1 and X 2 each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom is preferred, and the number of carbon atoms is 1 More preferably, the perfluoroalkyl group of ～10 is more preferably a perfluoroalkyl group having 1 to 4 carbon atoms, and a trifluoromethyl group is particularly preferred.

【化學式8】 [Chemical Formula 8]

式（AN-2）中，X3 、X4 以及X5 分別獨立地表示氟原子或碳原子數1～10的具有氟原子之烷基。 X3 、X4 以及X5 分別獨立地與X1 以及X2 的含義相同，較佳之範圍亦相同。In the formula (AN-2), X 3 , X 4 and X 5 each independently represent a fluorine atom or an alkyl group having a fluorine atom and having 1 to 10 carbon atoms. X 3 , X 4 and X 5 are each independently the same as X 1 and X 2 , and the preferred range is also the same.

【化學式9】 [Chemical Formula 9]

式（AN-3）中，X6 表示碳原子數1～10的具有氟原子之烷基。 X6 為碳原子數1～10的全氟烷基為較佳，碳原子數1～4的全氟烷基為進一步較佳。 【化學式10】 In the formula (AN-3), X 6 represents an alkyl group having a fluorine atom and having 1 to 10 carbon atoms. X 6 is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. [Chemical Formula 10]

式（AN-4）中，X7 表示碳原子數1～10的具有氟原子之伸烷基。 X7 為碳原子數1～10的全氟伸烷基為較佳，碳原子數1～4的全氟伸烷基為進一步較佳。In the formula (AN-4), X 7 represents an alkylene group having a fluorine atom and having 1 to 10 carbon atoms. X 7 is preferably a perfluoroalkylene group having 1 to 10 carbon atoms, and a perfluoroalkylene group having 1 to 4 carbon atoms is further more preferable.

【化學式11】 [Chemical Formula 11]

式（AN-5）中，Ar1 、Ar2 、Ar3 以及Ar4 分別獨立地表示芳基。 Ar1 、Ar2 、Ar3 以及Ar4 分別獨立地為碳原子數6～20的芳基為較佳，碳原子數6～14的芳基為更佳，碳原子數6～10的芳基為進一步較佳。 Ar1 、Ar2 、Ar3 以及Ar4 所表示之芳基可以具有取代基。在具有取代基的情況下，可以舉出鹵素原子、烷基、芳基、烷氧基、羰基、羰氧基、胺基甲醯基、磺酸基、磺醯胺基、硝基等，鹵素原子以及烷基為較佳，氟原子、烷基為更佳，氟原子、碳原子數1～4的全氟烷基為進一步較佳。 Ar1 、Ar2 、Ar3 以及Ar4 分別獨立地為含有鹵素原子和/或具有鹵素原子之烷基之苯基為更佳，含有氟原子和/或具有氟之烷基之苯基為進一步較佳。In the formula (AN-5), Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represent an aryl group. Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently an aryl group having 6 to 20 carbon atoms, and an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is preferable. It is further preferred. The aryl group represented by Ar 1 , Ar 2 , Ar 3 and Ar 4 may have a substituent. In the case of having a substituent, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, an aminomethyl fluorenyl group, a sulfonic acid group, a sulfonylamino group, a nitro group, etc., may be mentioned. The atom and the alkyl group are preferably a fluorine atom or an alkyl group, and a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is more preferable. Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently a phenyl group containing a halogen atom and/or an alkyl group having a halogen atom, and a phenyl group containing a fluorine atom and/or an alkyl group having fluorine is further Preferably.

非親核性的對陰離子又為-B（CN）n1 （ORa ）4-n1 （Ra 表示碳原子數1～10的烷基或碳原子數6～10的芳基，n1表示1～4的整數）為較佳。作為碳原子數1～10的烷基的Ra 為碳原子數1～6的烷基為較佳，碳原子數1～4的烷基為更佳。作為碳原子數6～10的芳基的Ra 為苯基、萘基為較佳。 n1為1～3為較佳，1～2為更佳。The non-nucleophilic counter anion is -B(CN) n1 (OR a ) 4-n1 (R a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 represents 1 to 1). An integer of 4 is preferred. R a of the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. R a which is an aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group. It is preferable that n1 is 1 to 3, and 1 to 2 is more preferable.

非親核性的對陰離子又進一步為-PF6 RP (6-n2) - （RP 表示碳原子數1～10的氟化烷基，n2表示1～6的整數）為較佳。RP 為碳原子數1～6的具有氟原子之烷基為較佳，碳原子數1～4的具有氟原子之烷基為更佳，碳原子數1～3的全氟烷基為進一步較佳。 n2為1～4的整數為較佳，1或2為更佳。The non-nucleophilic counter anion is further preferably -PF 6 R P (6-n2) - (R P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n 2 represents an integer of 1 to 6). R P is preferably an alkyl group having a fluorine atom having 1 to 6 carbon atoms, more preferably an alkyl group having a fluorine atom having 1 to 4 carbon atoms, and a perfluoroalkyl group having 1 to 3 carbon atoms is further Preferably. An integer of n2 is preferably from 1 to 4, more preferably 1 or 2.

非親核性對陰離子的每1分子的質量為100～1,000為較佳，200～500為更佳。 以下，示出非親核性的對陰離子的具體例，但本發明係不限定於此者。The non-nucleophilic property is preferably from 100 to 1,000 per molecule of the anion, more preferably from 200 to 500. Specific examples of the non-nucleophilic counter anion are shown below, but the present invention is not limited thereto.

【化學式12】【化學式13】【化學式14】【化學式15】 [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15]

（色素多聚物） 接著，對色素多聚物的較佳實施形態進行說明。以下，將三芳基甲烷骨架和呫噸骨架還合稱為色素骨架。 作為具有三芳基甲烷骨架之色素（色素A）為多聚物時的具體例，可以舉出日本特開2015-83652號公報中記載之化合物。該內容編入本說明書中。又，色素多聚物的製造方法無特別限定，適當地選擇合適的方式即可，例如能夠利用日本特開2015-83652號公報中記載之方法製造。 在本發明中，色素多聚物為具有由後述通式（A）表示之重複單元之色素多聚物（亦稱作色素多聚物（A））、具有由後述通式（B）表示之重複單元之色素多聚物（亦稱作色素多聚物（B））、具有由後述通式（C）表示之重複單元之色素多聚物（亦稱作色素多聚物（C））以及由通式（D）表示之色素多聚物（亦稱作色素多聚物（D））為較佳。色素多聚物（A）、色素多聚物（C）以及色素多聚物（D）為更佳，從容易獲得可靠性優異之硬化膜的理由來看，色素多聚物（A）以及色素多聚物（D）為特佳。以下，對色素多聚物進行詳細說明。(Pigment Polymer) Next, a preferred embodiment of the dye polymer will be described. Hereinafter, the triarylmethane skeleton and the xanthene skeleton are collectively referred to as a pigment skeleton. Specific examples of the case where the dye (pigment A) having a triarylmethane skeleton is a polymer is a compound described in JP-A-2015-83652. This content is incorporated in this specification. In addition, the method of producing the dye polymer is not particularly limited, and an appropriate method may be appropriately selected, and for example, it can be produced by the method described in JP-A-2015-83652. In the present invention, the dye polymer is a dye polymer (also referred to as a dye polymer (A)) having a repeating unit represented by the following formula (A), and has a formula (B) which will be described later. a dye multimer (also referred to as a dye polymer (B)) of a repeating unit, a dye polymer (also referred to as a dye polymer (C)) having a repeating unit represented by the following formula (C), and The dye polymer (also referred to as the dye polymer (D)) represented by the formula (D) is preferred. The dye polymer (A), the dye polymer (C), and the dye polymer (D) are more preferable, and the dye polymer (A) and the pigment are considered from the viewpoint of easily obtaining a cured film having excellent reliability. The polymer (D) is particularly preferred. Hereinafter, the dye polymer will be described in detail.

＜＜＜色素多聚物（A）＞＞＞ 色素多聚物（A）含有由下述通式（A）表示之重複單元。色素多聚物（A）中，由下述通式（A）表示之重複單元的比例為構成色素多聚物之總重複單元的10～100質量%為較佳。下限為20質量%以上為更佳，30質量%以上為進一步較佳，50質量%以上為特佳。上限為95質量%以下為更佳。 【化學式16】通式（A）中，X1 表示藉由聚合而形成之連結基，L1 表示單鍵或2價連結基。DyeI表示具有三芳基甲烷骨架或呫噸骨架之基團。<<<Pigment Polymer (A)>>> The dye polymer (A) contains a repeating unit represented by the following formula (A). In the dye polymer (A), the ratio of the repeating unit represented by the following formula (A) is preferably from 10 to 100% by mass based on the total repeating unit constituting the dye polymer. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit is preferably 95% by mass or less. [Chemical Formula 16] In the formula (A), X 1 represents a linking group formed by polymerization, and L 1 represents a single bond or a divalent linking group. DyeI represents a group having a triarylmethane skeleton or a xanthene skeleton.

通式（A）中，X1 表示藉由聚合而形成之連結基。亦即，X1 表示重複單元的主鏈。作為X1 ，只要是由公知的可聚合之單體形成之連結基，則無限制。可以舉出由下述（XX-1）～（XX-30）表示之連結基，由下述（XX-1）～（XX-24）表示之連結基為較佳，選自（XX-1）、（XX-2）、（XX-10）～（XX-17）、（XX-18）、（XX-19）以及（XX-24）為更佳，選自（XX-1）、（XX-2）、（XX-10）～（XX-17）以及（XX-24）為進一步較佳，選自（XX-1）、（XX-2）以及（XX-11）為特佳。 式中，用以*所示之部位表示與L1 連結。Me表示甲基。又，（XX-18）以及（XX-19）中的R表示氫原子、碳原子數1～5的烷基或苯基。In the formula (A), X 1 represents a linking group formed by polymerization. That is, X 1 represents the main chain of the repeating unit. X 1 is not limited as long as it is a linking group formed of a known polymerizable monomer. The linking group represented by the following (XX-1) to (XX-30) is preferable, and the linking group represented by the following (XX-1) to (XX-24) is preferable, and is selected from (XX-1). ), (XX-2), (XX-10) to (XX-17), (XX-18), (XX-19), and (XX-24) are more preferably selected from (XX-1), ( XX-2), (XX-10) to (XX-17), and (XX-24) are further preferably selected from (XX-1), (XX-2), and (XX-11). In the formula, the portion indicated by * indicates that it is linked to L 1 . Me represents a methyl group. Further, R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group.

【化學式17】【化學式18】 [Chemical Formula 17] [Chemical Formula 18]

L1 表示單鍵或2價連結基。作為2價連結基，可以舉出碳原子數1～30的伸烷基、碳原子數6～30的伸芳基、雜環連結基、-CH=CH-、-O-、-S-、-C（=O）-、-CO2 -、-NR-、-CONR-、-O2 C-、-SO-、-SO2 -以及連結2個以上該些而形成之連結基、由下述（L-1）表示之基團。在此，R表示氫原子、烷基、芳基或雜環基。 【化學式19】式（L-1）中，藉由由*1表示之部位與式（A）的X1 連結，藉由由*2表示之部位與式（A）的DyeI連結。L 1 represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an extended aryl group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH=CH-, -O-, and -S-. -C(=O)-, -CO 2 -, -NR-, -CONR-, -O 2 C-, -SO-, -SO 2 - and a linking group formed by linking two or more of these The group represented by (L-1). Here, R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. [Chemical Formula 19] In the formula (L-1), the moiety represented by *1 is linked to X 1 of the formula (A), and the moiety represented by *2 is linked to DyeI of the formula (A).

L11 表示單鍵或2價連結基。作為2價連結基，可以舉出碳原子數1～6的伸烷基、碳原子數6～18的伸芳基、-O-、-CO-、-S-、-SO2 -、-NRA RB -或由該些組合構成之基團等。伸烷基可以是直鏈狀、支鏈狀或環狀中的任一種。伸芳基可以為單環，亦可為多環。-NRA RB -中，RA 以及RB 分別獨立地表示氫原子或碳原子數1～6的烷基，RA 以及RB 可以相互鍵結而形成環。 L12 表示-SO2 -或-CO-。 L13 表示2價連結基。作為2價連結基，可以舉出用L11 説明之基團，碳原子數6～18的伸芳基（伸苯基為較佳）、-O-、-CO-、-S-、-NRA RB -或由該些組合構成之基團為較佳，由伸苯基、-O-以及-CO-的組合構成之基團為更佳。 G表示碳原子或氮原子。 G為碳原子時，n2表示1，G為氮原子時，n2表示0。 R7A 表示含有氟原子之伸烷基或含有氟原子之伸芳基。伸烷基的碳原子數為1～10為較佳，1～6為更佳，1～3為進一步較佳。伸芳基的碳原子數為6～20為較佳，6～14為更佳，6～10為進一步較佳。 R7B 表示含有氟原子之烷基或含有氟原子之芳基。烷基的碳原子數為1～10為較佳，1～6為更佳，1～3為進一步較佳。芳基的碳原子數為6～20為較佳，6～14為更佳，6～10為進一步較佳。L 11 represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 6 carbon atoms, an extended aryl group having 6 to 18 carbon atoms, -O-, -CO-, -S-, -SO 2 -, -NR. A R B - or a group consisting of such combinations. The alkylene group may be any of a linear chain, a branched chain or a cyclic chain. The aryl group may be a single ring or a multiple ring. In -NR A R B -, R A and R B each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R A and R B may be bonded to each other to form a ring. L 12 represents -SO 2 - or -CO-. L 13 represents a divalent linking group. Examples of the divalent linking group include a group described by L 11 , an extended aryl group having 6 to 18 carbon atoms (preferably, a phenyl group is preferred), -O-, -CO-, -S-, and -NR. A R B - or a group consisting of these combinations is preferred, and a group consisting of a combination of a phenyl group, -O- and -CO- is more preferred. G represents a carbon atom or a nitrogen atom. When G is a carbon atom, n2 represents 1, and when G is a nitrogen atom, n2 represents 0. R 7A represents an alkylene group containing a fluorine atom or an extended aryl group containing a fluorine atom. The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. The number of carbon atoms of the aryl group is preferably from 6 to 20, more preferably from 6 to 14, and further preferably from 6 to 10. R 7B represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and further preferably 6 to 10 carbon atoms.

含有由通式（A）表示之重複單元之色素多聚物能夠藉由如下方法合成：（1）藉由加成聚合而合成具有色素骨架之單體之方法；（2）使具有異氰酸酯基、酸酐基或環氧基等高反應性官能基之聚合物和具有能夠與高反應性基反應之官能基（羥基、一級或二級氨基、羧基等）之色素反應之方法。 加成聚合能夠應用公知的加成聚合（自由基聚合、陰離子聚合、陽離子聚合），但其中，尤其是藉由自由基聚合進行合成，能使反應條件溫和化，不會使色素骨架分解，故較佳。自由基聚合能夠應用公知的反應條件。 從耐熱性的觀點來看，具有由通式（A）表示之重複單元之色素多聚物為利用具有乙烯性不飽和键之色素單量體進行自由基聚合而得之自由基聚合物為較佳。The dye multimer containing the repeating unit represented by the general formula (A) can be synthesized by (1) a method of synthesizing a monomer having a pigment skeleton by addition polymerization; (2) having an isocyanate group, A method of reacting a polymer of a highly reactive functional group such as an acid anhydride group or an epoxy group with a dye having a functional group (hydroxyl group, primary or secondary amino group, carboxyl group, or the like) capable of reacting with a highly reactive group. Addition polymerization can employ a known addition polymerization (radical polymerization, anionic polymerization, cationic polymerization), but among them, especially by radical polymerization, the reaction conditions can be mildened without decomposing the pigment skeleton. Preferably. Free radical polymerization can employ well-known reaction conditions. From the viewpoint of heat resistance, the dye polymer having a repeating unit represented by the general formula (A) is a radical polymer obtained by radical polymerization using a dye single body having an ethylenically unsaturated bond. good.

（其他重複單元） 本發明中的色素多聚物除了含有由通式（A）表示之重複單元之外，亦可含有其他重複單元。其他重複單元可以含有聚合性基、酸基等官能基。亦可不含有官能基。色素多聚物具有選自具有酸基之重複單元以及具有聚合性基之重複單元之1種以上為較佳，含有具有酸基之重複單元為進一步較佳。(Other Repeating Unit) The dye polymer in the present invention may contain other repeating units in addition to the repeating unit represented by the general formula (A). Other repeating units may contain a functional group such as a polymerizable group or an acid group. It may also contain no functional groups. The dye polymer is preferably one or more selected from the group consisting of a repeating unit having an acid group and a repeating unit having a polymerizable group, and further preferably a repeating unit having an acid group.

作為聚合性基，可以舉出乙烯基、（甲基）烯丙基、（甲基）丙烯醯基以及（甲基）丙烯醯氧基，（甲基）丙烯醯基以及（甲基）丙烯醯氧基為較佳。 具有聚合性基之重複單元的比例為構成色素多聚物之總重複單元的0～50質量%為較佳。下限為1質量%以上為更佳，3質量%以上為進一步較佳。上限為35質量%以下為更佳，30質量%以下為進一步較佳。Examples of the polymerizable group include a vinyl group, a (meth)allyl group, a (meth)acryl fluorenyl group, a (meth)acryloxy group, a (meth)acryl fluorenyl group, and a (meth) acrylonitrile group. An oxy group is preferred. The proportion of the repeating unit having a polymerizable group is preferably from 0 to 50% by mass based on the total repeating unit constituting the dye polymer. The lower limit is preferably 1% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 35% by mass or less, and more preferably 30% by mass or less.

作為酸基，可例示羧基、磺酸基、磷酸基。酸基可以只含有1種，亦可含有2種以上。 具有酸基之重複單元的比例為構成色素多聚物之總重複單元的0～50質量%為較佳。下限為1質量%以上為更佳，3質量%以上為進一步較佳。上限為35質量%以下為更佳，30質量%以下為進一步較佳。The acid group may, for example, be a carboxyl group, a sulfonic acid group or a phosphoric acid group. The acid group may be contained alone or in combination of two or more. The ratio of the repeating unit having an acid group is preferably from 0 to 50% by mass based on the total repeating unit constituting the dye polymer. The lower limit is preferably 1% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 35% by mass or less, and more preferably 30% by mass or less.

作為其他官能基，可以舉出由2～20個無取代的伸烷氧基鏈的重複構成之基團、內酯、酸酐、醯胺、氰基等顯影促進基、長鏈以及環狀烷基、芳烷基、芳基、聚環氧烷基、羥基、馬來醯亞胺基、氨基等親疏水性調整基等，能夠適當地導入。 由2～20個無取代的伸烷氧基鏈的重複構成之基團中，伸烷氧基鏈的重複個數為2～10個為較佳，2～15個為更佳，2～10個為進一步較佳。1個伸烷氧基鏈用-（CH2 ）n O-表示，n為整數，但n為1～10為較佳，1～5為更佳，2或3為進一步較佳。Examples of the other functional group include a group consisting of a repeating group of 2 to 20 unsubstituted alkoxy groups, a developing accelerator such as a lactone, an acid anhydride, a guanamine or a cyano group, a long chain, and a cyclic alkyl group. A hydrophilic or hydrophobicity adjusting group such as an aralkyl group, an aryl group, a polyalkylene oxide group, a hydroxyl group, a maleimide group or an amino group can be appropriately introduced. In the group consisting of 2 to 20 repeating alkoxy chain repeats, the number of repeating alkoxy chains is preferably 2 to 10, more preferably 2 to 15, 2 to 10 It is further preferred. The one alkoxy chain is represented by -(CH 2 ) n O-, and n is an integer, but n is preferably from 1 to 10, more preferably from 1 to 5, still more preferably 2 or 3.

示出其他重複單元的具體例，但本發明係不限定於此者。 【化學式20】【化學式21】 Specific examples of other repeating units are shown, but the present invention is not limited thereto. [Chemical Formula 20] [Chemical Formula 21]

＜＜＜色素多聚物（B）＞＞＞ 色素多聚物（B）含有具有三芳基甲烷骨架或呫噸骨架之陽離子和由下述通式（B）表示之重複單元。色素多聚物（B）中，由下述通式（B）表示之重複單元的比例為構成色素多聚物之總重複單元的10～100質量%為較佳。下限為20質量%以上為更佳，30質量%以上為進一步較佳，50質量%以上為特佳。上限為95質量%以下為更佳。 【化學式22】通式（B）中，X2 表示藉由聚合而形成之連結基，L2 表示單鍵或2價連結基，Z表示陰離子。<<<Pigment Polymer (B)>>> The dye polymer (B) contains a cation having a triarylmethane skeleton or a xanthene skeleton and a repeating unit represented by the following formula (B). In the dye multimer (B), the ratio of the repeating unit represented by the following formula (B) is preferably from 10 to 100% by mass based on the total repeating unit constituting the dye polymer. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit is preferably 95% by mass or less. [Chemical Formula 22] In the formula (B), X 2 represents a linking group formed by polymerization, L 2 represents a single bond or a divalent linking group, and Z represents an anion.

X2 與通式（A）的X1 相同含義，較佳範圍亦相同。 L2 表示單鍵或2價連結基。作為2價連結基，可例示烴基、-NH-、-CO-、-COO-以及含有色素骨架之2價基等，可以舉出碳原子數1～20的伸烷基、碳原子數6～20的伸芳基、碳原子數4～20的雜環基、碳原子數1～20的烷基磺醯基、碳原子數6～20的芳基磺醯基、碳原子數1～20的烷羰基、碳原子數6～20的芳羰基、碳原子數1～20的烷基氨基、碳原子數6～20的芳基氨基、碳原子數1～2的烷羰氧基、碳原子數6～20的芳羰氧基等。該些2價連結基由電子吸引性基取代為較佳，作為電子吸引性基，可以舉出鹵素原子（氟原子、氯原子、溴原子、碘原子）、硝基、氰基、鹵化烷基（例如三氟甲基）、鹵化芳基。 Z表示陰離子。作為陰離子無特別限定，但可以舉出-SO3 - 、-COO- 、-PO4 - 、雙（磺醯基）亞胺陰離子、三（磺醯基）甲基化物陰離子以及四芳基硼酸鹽陰離子等。又，由通式（Z-1）表示之陰離子、由通式（Z-2）表示之陰離子、由下述通式（Z-3）表示之陰離子亦較佳。 作為Z，由通式（Z-1）～（Z-3）表示之陰離子為較佳，由通式（2-1）表示之基團、氟化烷基磺醯亞胺基（通式（2-2）中，Y2 表示氮原子，A2 表示氟化烷基磺醯基）或氟化烷基磺甲基化物基（通式（2-2）中，Y2 表示碳原子，A2 表示氟化烷基磺醯基）為特佳。X 2 has the same meaning as X 1 of the general formula (A), and the preferred range is also the same. L 2 represents a single bond or a divalent linking group. Examples of the divalent linking group include a hydrocarbon group, -NH-, -CO-, -COO-, and a divalent group containing a dye skeleton, and examples thereof include an alkylene group having 1 to 20 carbon atoms and 6 to 6 carbon atoms. a aryl group of 20, a heterocyclic group having 4 to 20 carbon atoms, an alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, or a carbon number of 1 to 20; An alkylcarbonyl group, an aromatic carbonyl group having 6 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, an alkylcarbonyloxy group having 1 to 2 carbon atoms, and a carbon number 6 to 20 arylcarbonyloxy groups and the like. These divalent linking groups are preferably substituted by an electron attracting group, and examples of the electron attracting group include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a nitro group, a cyano group, and an alkyl halide group. (e.g., trifluoromethyl), halogenated aryl. Z represents an anion. The anion is not particularly limited, and examples thereof include -SO 3 - , -COO - , -PO 4 - , bis(sulfonyl)imide anion, tris(sulfonyl)methide anion, and tetraarylborate. Anion, etc. Further, an anion represented by the formula (Z-1), an anion represented by the formula (Z-2), and an anion represented by the following formula (Z-3) are also preferred. As Z, an anion represented by the general formulae (Z-1) to (Z-3) is preferred, and a group represented by the formula (2-1), a fluorinated alkylsulfonimide group (general formula ( In 2-2), Y 2 represents a nitrogen atom, A 2 represents a fluorinated alkylsulfonyl group or a fluorinated alkylsulfonylmethyl group (in the formula (2-2), Y 2 represents a carbon atom, A 2 represents a fluorinated alkylsulfonyl group).

通式（Z-1） *-Y1 -A1 （通式（Z-1）中，*表示與通式（B）中的L2 的鍵結部位，Y1 表示氟化伸烷基，A1 表示SO3 - 。）Formula (Z-1) *-Y 1 -A 1 (In the formula (Z-1), * represents a bonding site with L 2 in the formula (B), and Y 1 represents a fluorinated alkyl group, A 1 represents SO 3 - .)

通式（Z-1）中，Y1 表示氟化伸烷基。氟化伸烷基的碳原子數為1～20為較佳，1～10為更佳，1～6為進一步較佳。又，全氟伸烷基為更佳。In the formula (Z-1), Y 1 represents a fluorinated alkyl group. The fluorinated alkyl group has preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms. Further, a perfluoroalkylene group is more preferable.

通式（Z-2） *-Y2 -（A2 ）n 通式（Z-2）中，*表示與通式（B）中的L2 的鍵結部位。 Y2 表示由硼原子、碳原子、氮原子或磷原子構成之陰離子。 在Y2 為硼原子的情況下，n為3，A2 為含有鹵素原子、氰基、氟原子以及氰基的至少1個之烷基或含有氟原子以及氰基的至少1個之芳基為較佳。 在Y2 為碳原子的情況下，n為2，A2 為含有鹵素原子、氰基、氟原子以及氰基的至少1個之烷基、含有氟原子以及氰基的至少1個之芳基、可以含有氟原子以及氰基的至少1個之烷基磺醯基或可以含有氟原子以及氰基的至少1個之芳基磺醯基為較佳。2個A2 可以相互鍵結而形成環。 在Y2 為氮原子的情況下，n為1，A2 為含有氟原子以及氰基的至少1個之烷基、含有氟原子以及氰基的至少1個之芳基、可以含有氟原子以及氰基的至少1個之烷基磺醯基或可以含有氟原子以及氰基的至少1個之芳基磺醯基為較佳。 在Y2 為磷原子的情況下，n為1或3，A2 為含有氟原子以及氰基的至少1個之烷基、含有氟原子以及氰基的至少1個之芳基、可以含有氟原子以及氰基的至少1個之烷基磺醯基或可以含有氟原子以及氰基的至少1個之芳基磺醯基為較佳。 在n為2以上的情況下，複數個A2 可以相同，亦可不同。In the formula (Z-2) *-Y 2 -(A 2 ) n In the formula (Z-2), * represents a bonding site with L 2 in the formula (B). Y 2 represents an anion composed of a boron atom, a carbon atom, a nitrogen atom or a phosphorus atom. In the case where Y 2 is a boron atom, n is 3, and A 2 is at least one alkyl group containing a halogen atom, a cyano group, a fluorine atom, and a cyano group, or at least one aryl group containing a fluorine atom and a cyano group. It is better. In the case where Y 2 is a carbon atom, n is 2, and A 2 is at least one alkyl group containing a halogen atom, a cyano group, a fluorine atom, and a cyano group, and at least one aryl group containing a fluorine atom and a cyano group. At least one alkylsulfonyl group which may contain a fluorine atom and a cyano group, or at least one arylsulfonyl group which may contain a fluorine atom and a cyano group is preferable. Two A 2 groups may be bonded to each other to form a ring. When Y 2 is a nitrogen atom, n is 1, and A 2 is at least one alkyl group containing a fluorine atom and a cyano group, at least one aryl group containing a fluorine atom and a cyano group, and may contain a fluorine atom and It is preferred that at least one alkylsulfonyl group of the cyano group or at least one arylsulfonyl group which may contain a fluorine atom and a cyano group. When Y 2 is a phosphorus atom, n is 1 or 3, and A 2 is at least one alkyl group containing a fluorine atom and a cyano group, at least one aryl group containing a fluorine atom and a cyano group, and may contain fluorine. It is preferred that at least one alkylsulfonyl group of an atom and a cyano group or at least one arylsulfonyl group which may contain a fluorine atom and a cyano group. When n is 2 or more, a plurality of A 2 's may be the same or different.

在通式（Z-1）以及通式（Z-2）含有氟原子的情況下，Z所含之氟原子相對於構成Z之總原子數之比例為5～80%為較佳，10～70%為更佳。When the general formula (Z-1) and the general formula (Z-2) contain a fluorine atom, the ratio of the fluorine atom contained in Z to the total number of atoms constituting Z is preferably 5 to 80%, preferably 10 to 10%. 70% is better.

通式（Z-3） 【化學式23】通式（Z-3）中，*表示與通式（B）中的L2 的鍵結部位。 R1 ～R4 分別獨立地為氰基或氟化烷基為較佳。General formula (Z-3) [Chemical Formula 23] In the general formula (Z-3), * represents a bonding site with L 2 in the general formula (B). R 1 to R 4 are each independently a cyano group or a fluorinated alkyl group.

作為由通式（B）表示之重複單元的具體例，可以舉出日本特開2014-199436號公報的段落號0162～0166中記載之結構。Specific examples of the repeating unit represented by the general formula (B) include the structures described in paragraphs 0162 to 0166 of JP-A-2014-199436.

色素多聚物（B）除了含有由通式（B）表示之重複單元之外，亦可含有在色素多聚物（A）中說明之其他重複單元等。又，亦可進一步含有由上述通式（A）表示之重複單元以及由後述通式（C）表示之重複單元。The dye polymer (B) may contain, in addition to the repeating unit represented by the formula (B), other repeating units described in the dye polymer (A). Further, it may further contain a repeating unit represented by the above formula (A) and a repeating unit represented by the following formula (C).

＜＜＜色素多聚物（C）＞＞＞ 色素多聚物（C）含有由下述通式（C）表示之重複單元。色素多聚物（C）中，由下述通式（C）表示之重複單元的比例為構成色素多聚物之總重複單元的10～100質量%為較佳。下限為20質量%以上為更佳，30質量%以上為進一步較佳，50質量%以上為特佳。上限為95質量%以下為更佳。 【化學式24】通式（C）中，L3 表示單鍵或2價連結基。DyeIII表示具有三芳基甲烷骨架或呫噸骨架之基團。m表示0或1。<<<Pigment Polymer (C)>>> The dye polymer (C) contains a repeating unit represented by the following formula (C). In the dye polymer (C), the ratio of the repeating unit represented by the following formula (C) is preferably from 10 to 100% by mass based on the total repeating unit constituting the dye polymer. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit is preferably 95% by mass or less. [Chemical Formula 24] In the formula (C), L 3 represents a single bond or a divalent linking group. DyeIII represents a group having a triarylmethane skeleton or a xanthene skeleton. m represents 0 or 1.

通式（C）中，L3 表示單鍵或2價連結基。作為由L3 表示之2價連結基，可以適宜地舉出碳原子數1～30的伸烷基、碳原子數6～30的伸芳基、雜環連結基、-CH=CH-、-O-、-S-、-C（=O）-、-CO2 -、-NR-、-CONR-、-O2 C-、-SO-、-SO2 -以及連結2個以上該些而形成之連結基。 m表示0或1，但1為較佳。In the formula (C), L 3 represents a single bond or a divalent linking group. The divalent linking group represented by L 3 may, for example, be an alkylene group having 1 to 30 carbon atoms, an extended aryl group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH=CH-, or O-, -S-, -C(=O)-, -CO 2 -, -NR-, -CONR-, -O 2 C-, -SO-, -SO 2 - and linking two or more of these The linking group formed. m represents 0 or 1, but 1 is preferred.

關於通式（C）的詳細內容，能夠參閱日本特開2013-29760號公報的段落號0165～0167、日本特開2015-57487號公報的段落號0080～0088的記載，該內容編入本申請說明書中。The details of the general formula (C) can be referred to in paragraphs 0065 to 0167 of JP-A-2013-29760, and paragraphs 0080 to 0088 of JP-A-2015-57487, which is incorporated herein by reference. in.

作為由通式（C）表示之重複單元的具體例，可以舉出以下。 【化學式25】【化學式26】 Specific examples of the repeating unit represented by the general formula (C) include the following. [Chemical Formula 25] [Chemical Formula 26]

色素多聚物（C）除了含有由通式（C）表示之重複單元之外，亦可含有在色素多聚物（A）說明之其他重複單元。The dye polymer (C) may contain other repeating units described in the dye polymer (A) in addition to the repeating unit represented by the general formula (C).

色素多聚物（C）能夠藉由逐步聚合進行合成。逐步聚合可以舉出加聚（例如，二異氰酸酯化合物與二醇的反應、二環氧化合物與二羧酸的反應、四羧酸二酐與二醇的反應等）以及縮聚（例如，二羧酸與二醇的反應、二羧酸與二胺的反應等）。其中，尤其是藉由加聚反應進行之合成能夠使反應條件溫和化，不會使色素骨架分解，故較佳。在逐步聚合中能夠應用公知的反應條件。The pigment multipolymer (C) can be synthesized by stepwise polymerization. The stepwise polymerization may be an addition polymerization (for example, a reaction of a diisocyanate compound with a diol, a reaction of a diepoxy compound with a dicarboxylic acid, a reaction of a tetracarboxylic dianhydride with a diol, etc.) and polycondensation (for example, a dicarboxylic acid). Reaction with a diol, reaction of a dicarboxylic acid with a diamine, etc.). Among them, in particular, the synthesis by the addition polymerization reaction can make the reaction conditions mild, and it is preferable since the pigment skeleton is not decomposed. Well-known reaction conditions can be applied in the stepwise polymerization.

＜＜＜色素多聚物（D）＞＞＞ 色素多聚物（D）用通式（D）表示。 【化學式27】通式（D）中，L4 表示n價連結基。n表示2～20的整數。DyeIV表示含有具有三芳基甲烷骨架或者呫噸骨架之基團或具有三芳基甲烷骨架或者呫噸骨架之重複單元之聚合物鏈。<<<Pigment Polymer (D)>>> The dye polymer (D) is represented by the formula (D). [Chemical Formula 27] In the formula (D), L 4 represents an n-valent linking group. n represents an integer of 2 to 20. DyeIV denotes a polymer chain containing a group having a triarylmethane skeleton or a xanthene skeleton or a repeating unit having a triarylmethane skeleton or a xanthene skeleton.

通式（D）中，n為2～15為較佳，2～14為更佳，2～8為進一步較佳，2～7為特佳，2～6為最佳。 另外，1個色素中的n為整數，但本發明的著色組成物亦可含有複數個不同n者作為色素多聚物（D）。因此，本發明的著色組成物中的n的平均値有時不是整數。 在本發明中，1個色素中的n表示2～20的整數為較佳。 又，在色素多聚物（D）為將通式（D）中的n為2之色素a1含有50質量%、將n為1的色素a2含有50質量%之混合物的情況下，雖然n的平均値為1.5，但該混合物所含之上述色素a1由於n滿足2～20的整數，故相當於色素多聚物（D）。 又，在色素多聚物（D）為複數個色素多聚物（D）的混合物的情況下，n的平均値為2～20的數為較佳。In the formula (D), n is preferably 2 to 15, more preferably 2 to 14, 2 to 8 is further preferred, 2 to 7 is particularly preferred, and 2 to 6 is most preferred. Further, n of the one coloring matter is an integer, but the coloring composition of the present invention may contain a plurality of different n as the dye polymer (D). Therefore, the average enthalpy of n in the colored composition of the present invention is sometimes not an integer. In the present invention, n in one dye is preferably an integer of 2 to 20. In addition, when the dye polymer (D) is a mixture containing 50% by mass of the pigment a1 having n of 2 in the general formula (D) and 50% by mass of the pigment a2 having n being 1, the n is The average enthalpy is 1.5, but the pigment a1 contained in the mixture corresponds to an integer of 2 to 20, and corresponds to the dye polymer (D). Further, when the dye polymer (D) is a mixture of a plurality of dye polymers (D), the average 値 of n is preferably from 2 to 20.

L4 表示n價連結基。作為n價連結基，包括由1個至100個碳原子、0個至10個氮原子、0個至50個氧原子、1個至200個氫原子以及0個至20個硫原子構成之基團，即便無取代，亦可進一步含有取代基。 作為n價連結基的具體例，能夠舉出下述結構單元或將以下結構單元組合2個以上而構成之基團（亦可形成環結構）。L 4 represents an n-valent linking group. The n-valent linking group includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. The group, even if it is unsubstituted, may further contain a substituent. Specific examples of the n-valent linking group include the following structural units or a combination of two or more of the following structural units (which may also form a ring structure).

【化學式28】 [Chemical Formula 28]

以下示出n價連結基的具體例。但是，本發明中，係不限定於該些者。又，亦可以舉出日本特開2008-222950號公報的段落號0071～0072中記載之連結基、日本特開2013-029760號公報的段落號0176中記載之連結基。Specific examples of the n-valent linking group are shown below. However, in the present invention, it is not limited to these. In addition, the linking group described in paragraphs 0071 to 0072 of JP-A-2008-222950, and the linking group described in paragraph 0176 of JP-A-2013-029760 may be mentioned.

【化學式29】【化學式30】【化學式31】【化學式32】 [Chemical Formula 29] [Chemical Formula 30] [Chemical Formula 31] [Chemical Formula 32]

色素多聚物（D）用通式（D1）表示亦較佳。 【化學式33】通式（D）中，L4 表示n價連結基。n表示2～20的整數。DyeIVa表示含有具有三芳基甲烷骨架或者呫噸骨架之基團或具有三芳基甲烷骨架或者呫噸骨架之重複單元之聚合物鏈。S表示硫原子。The dye polymer (D) is also preferably represented by the formula (D1). [Chemical Formula 33] In the formula (D), L 4 represents an n-valent linking group. n represents an integer of 2 to 20. DyeIVa denotes a polymer chain containing a group having a triarylmethane skeleton or a xanthene skeleton or a repeating unit having a triarylmethane skeleton or a xanthene skeleton. S represents a sulfur atom.

（色素多聚物（D）的較佳態樣1） 色素多聚物（D）的較佳態樣之一可以舉出由下述通式（D-1）表示之結構。 （D-R2 ）n -R1 -（L1 -P）m ……（D-1） 通式（D-1）中，R1 表示（m+n）價連結基， P表示具有重複單元之1價取代基， D表示色素骨架， R2 以及L1 分別獨立地表示單鍵或2價連結基， m表示1～13的整數， 在m為1的情況下，P表示具有2個以上重複單元之1價取代基， 在m為2以上的情況下，複數個P可以互不相同，構成複數個P之重複單元的個數的平均値為2個以上， n表示2～14的整數， 在n為2以上的情況下，複數個D可以互不相同， m+n表示2～15的整數。(Preferred Aspect of Pigment Polymer (D) 1) One of the preferable aspects of the dye polymer (D) is a structure represented by the following formula (D-1). (DR 2 ) n -R 1 -(L 1 -P) m (D-1) In the formula (D-1), R 1 represents a (m+n) valent linking group, and P represents a repeating unit. a monovalent substituent, D represents a dye skeleton, and R 2 and L 1 each independently represent a single bond or a divalent linking group, and m represents an integer of 1 to 13, and when m is 1, P represents two or more repeats. When the m is 2 or more, the plural P may be different from each other, and the average number of repeating units constituting the plurality of P is two or more, and n represents an integer of 2 to 14, When n is 2 or more, a plurality of Ds may be different from each other, and m+n represents an integer of 2-15.

通式（D-1）中，m表示1～13的整數。m為1～5為較佳，1～4為更佳，1～3為特佳。 通式（D-1）中，n表示2～14的整數。n為2～8為較佳，2～7為更佳，2～6為特佳，2～5為進一步較佳。 通式（D-1）中，m+n為2～15為較佳。 雖然1個色素中的m以及n分別為整數，但在本發明中，通式（D-1）中的m、n可以含有複數個不同之色素多聚物。因此，本發明的著色組成物中的m以及n的平均値有時不是整數。在本發明中，1個色素中的m表示1～13的整數為較佳。又，在色素多聚物（D）為複數個色素多聚物（D）的混合物的情況下，m的平均値表示1～13，n的平均値表示2～14為較佳。In the formula (D-1), m represents an integer of 1 to 13. m is preferably from 1 to 5, more preferably from 1 to 4, and particularly preferably from 1 to 3. In the formula (D-1), n represents an integer of 2 to 14. n is preferably 2 to 8, more preferably 2 to 7, 2 to 6 is particularly preferred, and 2 to 5 is further preferred. In the formula (D-1), m+n is preferably from 2 to 15. Although m and n in one dye are each an integer, in the present invention, m and n in the formula (D-1) may contain a plurality of different dye polymers. Therefore, the average enthalpy of m and n in the colored composition of the present invention is sometimes not an integer. In the present invention, m in one dye is preferably an integer of from 1 to 13. Further, when the dye polymer (D) is a mixture of a plurality of dye polymers (D), the average 値 of m represents 1 to 13, and the average 値 of n represents 2 to 14 is preferable.

通式（D-1）中，R1 表示（m+n）價連結基。m+n滿足2～15。 作為由R1 表示之（m+n）價連結基，含有由1至100個碳原子、0個至10個氮原子、0個至50個氧原子、1個至200個氫原子以及0個至20個硫原子構成之基團，即便無取代，亦可進一步具有取代基。作為R1 所表示之（m+n）價連結基的具體例，可以舉出用上述L4 說明之結構。In the formula (D-1), R 1 represents a (m+n) valent linking group. m+n satisfies 2-15. As the (m+n) valent linking group represented by R 1 , containing 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 A group composed of up to 20 sulfur atoms may further have a substituent even if it is unsubstituted. Specific examples of the (m+n)-valent linking group represented by R 1 include the structures described in the above L 4 .

通式（D-1）中，R2 以及L1 分別獨立地表示單鍵或2價連結基。在R2 以及L1 存在複數個情況下，可以相同，亦可不同。 作為2價連結基，含有由1至100個碳原子、0個至10個氮原子、0個至50個氧原子、1個至200個氫原子以及0個至20個硫原子構成之基團，即便無取代，亦可進一步具有取代基。In the formula (D-1), R 2 and L 1 each independently represent a single bond or a divalent linking group. In the case where there are a plurality of R 2 and L 1 , they may be the same or different. a divalent linking group having a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms Even if it is unsubstituted, it may further have a substituent.

作為2價連結基的具體例，能夠舉出下述結構單元或將以下結構單元組合2個以上而構成之基團。R2 以及L1 為含有-S-之基團為較佳，-S-為更佳。Specific examples of the divalent linking group include the following structural units or a combination of two or more of the following structural units. R 2 and L 1 are preferably a group having -S-, and -S- is more preferred.

【化學式34】 [Chemical Formula 34]

通式（D-1）中，P表示取代基。作為取代基，具有乙烯基化合物衍生的重複單元之1價取代基為較佳。在m為2以上的情況下，m個P可以相同，亦可不同。 在m為1的情況下，P為具有2～20個（2～15個為較佳，2～10個為進一步較佳）乙烯基化合物衍生的重複單元之1價取代基為較佳。又，在m為2以上的情況下，m個P的乙烯基化合物衍生的重複單元的個數的平均値為2～20個（2～15個為較佳，2～10個為進一步較佳）為較佳。依該態樣，使塗佈膜的平坦性優化。 m為1時的P的重複單元的數，m為2以上的情況下，m個P的重複單元的個數的平均値能夠藉由核磁共振（NMR）求出。具體而言，例如根據由R1 表示之（m+n）價連結基與色素骨架D的峰面積比求出m，重複單元的峰面積比除以m，藉此能夠計算出。In the formula (D-1), P represents a substituent. As the substituent, a monovalent substituent having a vinyl compound-derived repeating unit is preferred. When m is 2 or more, m P's may be the same or different. In the case where m is 1, P is preferably a monovalent substituent having 2 to 20 (2 to 15 is preferred, 2 to 10 further preferred) vinyl compound-derived repeating units. Further, when m is 2 or more, the average number of repeating units derived from the vinyl compounds of m P is 2 to 20 (2 to 15 is preferred, and 2 to 10 is further preferred). ) is better. In this way, the flatness of the coating film is optimized. When the number of repeating units of P when m is 1, and m is 2 or more, the average enthalpy of the number of repeating units of m P can be obtained by nuclear magnetic resonance (NMR). Specifically, for example, m can be obtained from the peak area ratio of the (m+n) valent linking group represented by R 1 and the dye skeleton D, and the peak area ratio of the repeating unit is divided by m, whereby it can be calculated.

作為構成P之重複單元，可以舉出用上述色素多聚物（A）說明之其他重複單元。其他重複單元含有選自具有上述酸基之重複單元以及具有聚合性基之重複單元之1種以上為較佳，含有具有酸基之重複單元為進一步較佳。 在P含有具有酸基之重複單元的情況下，具有酸基之重複單元相對於P的總重複單元之比例為10～80莫耳%為較佳，10～65莫耳%為更佳。 在P含有具有聚合性基之重複單元的情況下，具有聚合性基之重複單元相對於P的總重複單元之比例為10～80莫耳%為較佳，10～65莫耳%為更佳。藉由P含有具有聚合性基之重複單元，能夠使色移性更加優化。Examples of the repeating unit constituting P include other repeating units described by the above dyed polymer (A). The other repeating unit preferably contains at least one selected from the group consisting of a repeating unit having the above acid group and a repeating unit having a polymerizable group, and a repeating unit having an acid group is further preferred. In the case where P contains a repeating unit having an acid group, the ratio of the repeating unit having an acid group to the total repeating unit of P is preferably from 10 to 80 mol%, more preferably from 10 to 65 mol%. In the case where P contains a repeating unit having a polymerizable group, the ratio of the repeating unit having a polymerizable group to the total repeating unit of P is preferably from 10 to 80 mol%, more preferably from 10 to 65 mol%. . The color shift property can be further optimized by the fact that P contains a repeating unit having a polymerizable group.

由上述通式（D-1）表示之具有色素骨架之色素多聚物能夠藉由下述方法等進行合成。 （1）使將選自羧基、羥基、氨基等之官能基導入至末端之聚合物以及具有色素骨架之酸鹵化物、具有色素骨架之烷基鹵化物或者具有色素骨架之異氰酸酯等進行高分子反應之方法。 （2）使將碳碳雙鍵導入至末端之聚合物和具有色素骨架之硫醇進行邁克爾加成反應之方法。 （3）使將碳碳雙鍵導入至末端之聚合物和具有色素骨架之硫醇，在自由基引發劑存在下進行反應之方法。 （4）使將複數個硫醇導入至末端之聚合物和具有碳碳雙鍵以及色素骨架之化合物，在自由基引發劑存在下進行反應之方法。 （5）在具有色素骨架之硫醇化合物的存在下，對乙烯基化合物進行自由基聚合之方法。 上述中，從合成的容易度考慮，（2）～（5）的合成方法為較佳，（3）～（5）的合成方法為更佳。The dye multimer having a dye skeleton represented by the above formula (D-1) can be synthesized by the following method or the like. (1) A polymer reaction is carried out by introducing a functional group selected from a carboxyl group, a hydroxyl group, an amino group or the like into a terminal, an acid halide having a dye skeleton, an alkyl halide having a dye skeleton, or an isocyanate having a pigment skeleton. The method. (2) A method of subjecting a polymer having a carbon-carbon double bond to a terminal and a thiol having a pigment skeleton to a Michael addition reaction. (3) A method of reacting a polymer having a carbon-carbon double bond to a terminal and a thiol having a dye skeleton in the presence of a radical initiator. (4) A method of reacting a polymer having a plurality of thiols introduced to a terminal and a compound having a carbon-carbon double bond and a pigment skeleton in the presence of a radical initiator. (5) A method of radically polymerizing a vinyl compound in the presence of a thiol compound having a pigment skeleton. Among the above, from the viewpoint of easiness of synthesis, the synthesis methods of (2) to (5) are preferred, and the synthesis methods of (3) to (5) are more preferable.

（色素多聚物（D）的較佳態樣2） 色素多聚物（D）的較佳態樣之一可以舉出由下述通式（D-2）表示之結構。 P-（Q）n ……（D-2） 通式（D-2）中，P表示n價連結基， Q表示含有具有色素骨架之重複單元之聚合物鏈， n個Q的具有色素骨架之重複單元的個數的平均値為2個以上， n表示3～10的整數。(Preferred Aspect 2 of the Pigment Polymer (D)) One of the preferable aspects of the dye polymer (D) is a structure represented by the following formula (D-2). P-(Q) n (D-2) In the formula (D-2), P represents an n-valent linking group, Q represents a polymer chain containing a repeating unit having a pigment skeleton, and n Q has a pigment skeleton The average number of repeating units is two or more, and n represents an integer of 3 to 10.

＜＜＜連結基P＞＞＞ 通式（D-2）中，P表示n價連結基。 作為n價連結基，含有由1個至100個碳原子、0個至10個氮原子、0個至50個氧原子、1個至200個氫原子以及0個至20個硫原子構成之基團，即便無取代，亦可進一步具有取代基。 P所表示之n價連結基為由1個至60個碳原子、0個至10個氮原子、0個至40個氧原子、1個至120個氫原子以及0個至10個硫原子構成之基團為較佳。由1個至50個碳原子、0個至10個氮原子、0個至30個氧原子、1個至100個氫原子以及0個至7個硫原子構成之基團為更佳。由1個至40個碳原子、0個至8個氮原子、0個至20個氧原子、1個至80個氫原子以及0個至5個硫原子構成之基團為進一步較佳。 P所表示之n價連結基為由多元醇衍生之連結基為較佳。<<<Linking Group P>>> In the formula (D-2), P represents an n-valent linking group. As the n-valent linking group, it contains a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. The group, even without substitution, may further have a substituent. The n-valent linking group represented by P is composed of 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0 to 10 sulfur atoms. The group is preferred. More preferably, the group consists of 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 sulfur atoms. A group consisting of 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms is further preferred. The n-valent linking group represented by P is preferably a linking group derived from a polyhydric alcohol.

由通式（D-2）表示之色素多聚物用通式（D-2a）表示為較佳。 【化學式35】通式（D-2a）中，A1 表示n價連結基， B1 表示單鍵、-O-、-S-、-CO-、-NR-、-O2 C-、-CO2 -、-NROC-或-CONR-， R表示氫原子、烷基或芳基， C1 表示單鍵或2價連結基， S表示硫原子， Q表示含有具有色素骨架之重複單元之聚合物鏈， n個Q的具有色素骨架之重複單元的個數的平均値為2個以上， n表示3～10的整數。The dye polymer represented by the formula (D-2) is preferably represented by the formula (D-2a). [Chemical Formula 35] In the formula (D-2a), A 1 represents an n-valent linking group, and B 1 represents a single bond, -O-, -S-, -CO-, -NR-, -O 2 C-, -CO 2 -, -NROC- or -CONR-, R represents a hydrogen atom, an alkyl group or an aryl group, C 1 represents a single bond or a divalent linking group, S represents a sulfur atom, and Q represents a polymer chain containing a repeating unit having a pigment skeleton, n The average number of repeating units having a pigment skeleton of Q is two or more, and n represents an integer of from 3 to 10.

通式（D-2a）中，A1 表示n價連結基。 作為n價連結基，由選自可以在主鏈具有氧原子之脂肪族烴基、芳香族環基以及雜環基之1種或2種以上的組合構成之基團為較佳。 作為脂肪族烴基，可以舉出伸烷基、伸烯基。伸烷基的碳原子數例如為1～60為較佳，1～30為更佳。伸烯基的碳原子數例如為1～60為較佳，1～30為更佳。 作為在主鏈具有氧原子之脂肪族烴基，可以舉出由-（ORx1 ）m -、-（Rx1 O）m -表示之基團。在主鏈具有氧原子之脂肪族烴基可以為直鏈、支鏈、環狀中的任一個。另外，主鏈係指連結基的骨架部分，不含有取代基。 Rx1 表示伸烷基或伸烯基。m表示1以上的整數，在m為2以上的情況下，m個Rx1 可以相同，亦可不同。 Rx1 所表示之伸烷基的碳原子數為1～20為較佳，1～10為更佳，1～5為進一步較佳。伸烷基可以為直鏈、支鏈、環狀中任一個。 Rx1 所表示之伸烯基的碳原子數為2～20為較佳，2～10為更佳，2～5為進一步較佳。伸烯基可以為直鏈、支鏈、環狀中的任一個。 芳香族環基可以為單環，亦可為多環。 雜環基為5員環或6員環為較佳。雜環基可以為單環，亦可為多環。作為雜環基所含有之雜原子，可例示氮原子、氧原子、硫原子。氮原子為較佳。雜原子的個數為1～3為較佳。In the formula (D-2a), A 1 represents an n-valent linking group. The n-valent linking group is preferably a group selected from the group consisting of an aliphatic hydrocarbon group having an oxygen atom in the main chain, an aromatic ring group, and a heterocyclic group, or a combination of two or more. Examples of the aliphatic hydrocarbon group include an alkylene group and an extended alkenyl group. The number of carbon atoms of the alkylene group is, for example, preferably from 1 to 60, more preferably from 1 to 30. The number of carbon atoms of the alkenyl group is preferably from 1 to 60, more preferably from 1 to 30. Examples of the aliphatic hydrocarbon group having an oxygen atom in the main chain include a group represented by -(OR x1 ) m - and -(R x1 O) m -. The aliphatic hydrocarbon group having an oxygen atom in the main chain may be any of a straight chain, a branched chain, and a cyclic group. Further, the main chain means a skeleton portion of a linking group and does not contain a substituent. R x1 represents an alkyl group or an alkenyl group. m represents an integer of 1 or more, and when m is 2 or more, m pieces of R x1 may be the same or different. The number of carbon atoms of the alkylene group represented by R x1 is preferably from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 5. The alkylene group may be any of a straight chain, a branched chain, and a cyclic chain. The number of carbon atoms of the alkenyl group represented by R x1 is preferably from 2 to 20, more preferably from 2 to 10, still more preferably from 2 to 5. The alkenyl group may be any of a straight chain, a branched chain, and a cyclic chain. The aromatic ring group may be a single ring or a polycyclic ring. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a polycyclic ring. The hetero atom contained in the heterocyclic group may, for example, be a nitrogen atom, an oxygen atom or a sulfur atom. A nitrogen atom is preferred. The number of hetero atoms is preferably from 1 to 3.

A1 所表示之n價連結基可以較佳地舉出可以在主鏈具有氧原子之烴基、芳香族環基、雜環基、可以在主鏈具有氧原子之烴基與芳香族環基的組合以及可以在主鏈具有氧原子之烴基與雜環基的組合等。The n-valent linking group represented by A 1 may preferably be a combination of a hydrocarbon group having an oxygen atom in the main chain, an aromatic ring group, a heterocyclic group, a hydrocarbon group having an oxygen atom in the main chain, and an aromatic ring group. And a combination of a hydrocarbon group having a oxygen atom in the main chain and a heterocyclic group.

通式（D-2a）中，B1 表示單鍵、-O-、-S-、-CO-、-NR-、-O2 C-、-CO2 -、-NROC-或-CONR-，單鍵、-O-、-CO-、-O2 C-、-CO2 -、-NROC-或-CONR-為較佳。 R表示氫原子、烷基或芳基。 R所表示之烷基的碳原子數為1～30為較佳，1～10為更佳。烷基可以為直鏈、支鏈、環狀中的任一個。 R所表示之芳基的碳原子數為6～30為較佳，6～12為更佳。 R為氫原子或烷基為較佳，氫原子為更佳。In the formula (D-2a), B 1 represents a single bond, -O-, -S-, -CO-, -NR-, -O 2 C-, -CO 2 -, -NROC- or -CONR-, A single bond, -O-, -CO-, -O 2 C-, -CO 2 -, -NROC- or -CONR- is preferred. R represents a hydrogen atom, an alkyl group or an aryl group. The alkyl group represented by R has preferably 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain. The aryl group represented by R has preferably 6 to 30 carbon atoms, more preferably 6 to 12 carbon atoms. R is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

通式（D-2a）中，C1 表示單鍵或2價連結基。 作為2價連結基，伸烷基、伸芳基、氧化烯基為較佳，伸烷基或氧化烯基為更佳。 伸烷基、氧化烯基的碳原子數為1～30為較佳，1～10為更佳。烷基、氧化烯基可以為直鏈、支鏈、環狀中的任一個。 伸芳基的碳原子數為6～30為較佳，6～12為更佳。In the formula (D-2a), C 1 represents a single bond or a divalent linking group. As the divalent linking group, an alkyl group, an aryl group or an oxyalkyl group is preferred, and an alkyl group or an oxyalkyl group is more preferred. The alkylene group and the oxyalkylene group preferably have 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group or the oxyalkylene group may be any of a straight chain, a branched chain, and a cyclic group. The number of carbon atoms of the aryl group is preferably from 6 to 30, more preferably from 6 to 12.

以下示出P所表示之n價連結基的具體例。但是，本發明中，係不限定於該些者。Specific examples of the n-valent linking group represented by P are shown below. However, in the present invention, it is not limited to these.

【化學式36】【化學式37】【化學式38】 [Chemical Formula 36] [Chemical Formula 37] [Chemical Formula 38]

Q所表示之聚合物鏈表示含有具有色素骨架之重複單元之聚合物鏈，n個Q的具有色素骨架之重複單元的個數的平均値為2個以上。n個Q可以相同，亦可不同。 Q所表示之聚合物鏈的具有色素骨架之重複單元的平均値為2～20個為較佳，2～15個為更佳，2～10個為進一步較佳。 具有色素骨架之重複單元的個數的平均値能夠藉由NMR（核磁共振）求出。具體而言，例如由由P表示之n價連結基與聚合物鏈Q的重複單元的峰面積比求出通式（D-2）中的重複單元的個數。接著，藉由重複單元的個數除以n，能夠計算出聚合物鏈Q中的重複單元的個數。 聚合物鏈Q的重量平均分子量為2000～40000為較佳。The polymer chain represented by Q represents a polymer chain containing a repeating unit having a dye skeleton, and the average number of repeating units having a pigment skeleton of n Q is two or more. n Qs may be the same or different. The average enthalpy of the repeating unit having a pigment skeleton of the polymer chain represented by Q is preferably 2 to 20, more preferably 2 to 15, and still more preferably 2 to 10. The average enthalpy of the number of repeating units having a pigment skeleton can be determined by NMR (nuclear magnetic resonance). Specifically, for example, the number of repeating units in the formula (D-2) is determined from the peak area ratio of the repeating unit of the n-valent linking group represented by P and the polymer chain Q. Next, the number of repeating units in the polymer chain Q can be calculated by dividing the number of repeating units by n. The weight average molecular weight of the polymer chain Q is preferably from 2,000 to 40,000.

Q所表示之聚合物鏈只要含有色素骨架，則係無特別規定者，但是為選自（甲基）丙烯酸系樹脂、苯乙烯系樹脂以及（甲基）丙烯酸/苯乙烯系樹脂之1種為較佳。 作為具有色素骨架之重複單元的骨架結構，雖然係無特別規定者，但可以舉出由上述通式（A）表示之重複單元、由上述通式（C）表示之重複單元等。又，構成聚合物鏈Q之總重複單元中的具有色素骨架之重複單元的合計為5～60莫耳%為較佳，10～50莫耳%為更佳，20～40莫耳%為進一步較佳。The polymer chain represented by Q is not particularly limited as long as it contains a pigment skeleton, but is one selected from the group consisting of a (meth)acrylic resin, a styrene resin, and a (meth)acrylic/styrene resin. Preferably. The skeleton structure having a repeating unit of the dye skeleton is not particularly limited, and examples thereof include a repeating unit represented by the above formula (A), a repeating unit represented by the above formula (C), and the like. Further, the total number of repeating units having a dye skeleton in the total repeating unit of the polymer chain Q is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol%. Preferably.

聚合物鏈Q除了含有具有上述色素骨架之重複單元之外，亦可含有在色素多聚物（A）中說明之其他重複單元等。作為其他重複單元，含有選自具有酸基之重複單元以及具有聚合性基之重複單元之1種以上為較佳。The polymer chain Q may contain, in addition to the repeating unit having the above-described dye skeleton, other repeating units described in the dye polymer (A). The other repeating unit is preferably one or more selected from the group consisting of a repeating unit having an acid group and a repeating unit having a polymerizable group.

在聚合物鏈Q含有具有聚合性基之重複單元的情況下，具有聚合性基之重複單元相對於聚合物鏈Q的總重複單元100莫耳之比例例如為5～50莫耳為較佳，10～40莫耳為更佳。 在聚合物鏈Q含有具有酸基之重複單元的情況下，具有酸基之重複單元相對於聚合物鏈Q的總重複單元100莫耳之比例例如為5～50莫耳為較佳，10～40莫耳為更佳。In the case where the polymer chain Q contains a repeating unit having a polymerizable group, the ratio of the repeating unit having a polymerizable group to the total repeating unit 100 of the polymer chain Q is, for example, preferably 5 to 50 mol. 10 to 40 moles is better. In the case where the polymer chain Q contains a repeating unit having an acid group, the ratio of the repeating unit having an acid group to the total repeating unit 100 of the polymer chain Q is preferably, for example, 5 to 50 mol, and 10 to 10 40 moles are better.

由上述通式（D-2）表示之色素多聚物無特別限制，能夠藉由對一分子中具有3～10個硫醇基之多官能硫醇化合物和具有色素骨架以及自由基聚合性基之化合物（自由基聚合性色素化合物）進行自由基聚合之方法而製成。 關於多官能硫醇化合物與自由基聚合性色素化合物的自由基聚合，例如能夠利用如下方法進行：將多官能硫醇化合物和自由基聚合性色素化合物溶解於適當的溶劑中，向該溶劑中添加自由基引發劑，在約50℃～100℃下使其進行加成之方法（硫醇-烯烴反應法）。The dye polymer represented by the above formula (D-2) is not particularly limited, and can be a polyfunctional thiol compound having 3 to 10 thiol groups in one molecule, and having a pigment skeleton and a radical polymerizable group. The compound (radical polymerizable dye compound) is produced by a method of radical polymerization. The radical polymerization of the polyfunctional thiol compound and the radically polymerizable dye compound can be carried out, for example, by dissolving a polyfunctional thiol compound and a radically polymerizable dye compound in an appropriate solvent, and adding the solvent to the solvent. A method in which a radical initiator is added at a temperature of from about 50 ° C to 100 ° C (thiol-olefin reaction method).

＜＜＜色素多聚物的諸性質＞＞＞ 色素多聚物的重量平均分子量（Mw）為2000～40000為較佳。下限為3000以上為更佳，4000以上為進一步較佳。上限為35000以下為更佳，30000以下為進一步較佳。藉由滿足上述範圍，耐溶劑性以及色移性變得更加良好。 在色素多聚物含有三芳基甲烷骨架的情況下，亦即在色素A為色素多聚物的情況下，色素A的重量平均分子量為2000～40000為較佳。下限為3000以上為更佳，4000以上為進一步較佳。上限為35000以下為更佳，30000以下為進一步較佳。 又，在色素多聚物含有呫噸骨架的情況下，亦即在色素B為色素多聚物的情況下，色素B的重量平均分子量為2000～40000為較佳。下限為3000以上為更佳，4000以上為進一步較佳。上限為35000以下為更佳，30000以下為進一步較佳。 另外，在本發明中，色素多聚物的重量平均分子量（Mw）為藉由凝膠滲透色譜法（GPC）測定獲得之聚苯乙烯換算値，具體而言，為利用後述之實施例中記載之方法測定之値。<<<Properties of Pigment Polymer>>> The weight average molecular weight (Mw) of the dye polymer is preferably from 2,000 to 40,000. The lower limit is preferably 3,000 or more, and more preferably 4,000 or more. The upper limit is preferably 35,000 or less, more preferably 30,000 or less. By satisfying the above range, solvent resistance and color shiftability are further improved. When the dye polymer contains a triarylmethane skeleton, that is, when the dye A is a dye polymer, the weight average molecular weight of the dye A is preferably from 2,000 to 40,000. The lower limit is preferably 3,000 or more, and more preferably 4,000 or more. The upper limit is preferably 35,000 or less, more preferably 30,000 or less. Further, when the dye polymer contains a xanthene skeleton, that is, when the dye B is a dye polymer, the weight average molecular weight of the dye B is preferably from 2,000 to 40,000. The lower limit is preferably 3,000 or more, and more preferably 4,000 or more. The upper limit is preferably 35,000 or less, more preferably 30,000 or less. Further, in the present invention, the weight average molecular weight (Mw) of the dye polymer is a polystyrene-converted enthalpy obtained by gel permeation chromatography (GPC) measurement, specifically, it is described in Examples described later. The method is determined by the method.

色素多聚物的酸值為10mgKOH/g以上為較佳，20mgKOH/g以上為更佳，27mgKOH/g以上為進一步較佳，30mgKOH/g以上為特佳。又，酸值的上限為300mgKOH/g以下為較佳，200mgKOH/g以下為更佳，180mgKOH/g以下為進一步較佳，130mgKOH/g以下為進一步較佳，120mgKOH/g以下為更進一步較佳。藉由滿足上述範圍，顯影性更加提高，可以更加降低顯影殘渣。The acid value of the dye polymer is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, further preferably 27 mgKOH/g or more, and particularly preferably 30 mgKOH/g or more. Further, the upper limit of the acid value is preferably 300 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 180 mgKOH/g or less, further preferably 130 mgKOH/g or less, and even more preferably 120 mgKOH/g or less. . By satisfying the above range, the developability is further improved, and the development residue can be further reduced.

色素多聚物的重量平均分子量（Mw）與數量平均分子量（Mn）之比〔（Mw）/（Mn）〕為1.0～3.0為較佳，1.0～2.5為進一步較佳，1.0～2.0為特佳。The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the dye polymer [(Mw)/(Mn)] is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and still more preferably 1.0 to 2.0. good.

＜＜其他著色劑＞＞ 本發明的著色組成物可以含有除了上述色素A以及色素B以外的其他著色劑。其他著色劑可以為染料以及顏料中的任一個。 又，其他著色劑可以為色素多聚物。色素多聚物的重量平均分子量為2,000～50,000為較佳，3,000～30,000為更佳，6,000～20,000為進一步較佳。 其他著色劑可以為1種，亦可為2種以上。<<Other Coloring Agent>> The coloring composition of the present invention may contain a coloring agent other than the above-described coloring matter A and coloring matter B. Other colorants may be any of a dye and a pigment. Further, other colorants may be pigment polymers. The weight average molecular weight of the dye polymer is preferably 2,000 to 50,000, more preferably 3,000 to 30,000, still more preferably 6,000 to 20,000. The other coloring agents may be used alone or in combination of two or more.

作為顏料，能夠舉出以往公知的各種無機顏料或有機顏料。又，若考慮高透射率為較佳這一點，不管是無機顏料，還是有機顏料，都使用平均粒徑盡可能小之顏料為較佳，若亦考慮處理性，則上述顏料的平均粒徑為0.01～0.1μm為較佳，0.01～0.05μm為更佳。Examples of the pigment include various conventional inorganic pigments or organic pigments. Further, in consideration of the fact that the high transmittance is preferable, it is preferable to use a pigment having an average particle diameter as small as possible, whether it is an inorganic pigment or an organic pigment, and if the handleability is also considered, the average particle diameter of the pigment is It is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.05 μm.

作為無機顏料，能夠舉出由金屬氧化物、金屬絡鹽等表示之金屬化合物，具體而言，能夠舉出碳黑、鈦黑等黑色顏料、鉄、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻等的金屬氧化物以及上述金屬的複合氧化物。Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like, and specific examples thereof include black pigments such as carbon black and titanium black, ruthenium, cobalt, aluminum, cadmium, lead, copper, and titanium. a metal oxide such as magnesium, chromium, zinc or bismuth or a composite oxide of the above metal.

作為有機顏料，能夠舉出以下者。但是，本發明係不限定於該些者。 C.I.顏料黃1、2、3、4、5、6、10、11、12、13、14、15、16、17、18、20、24、31、32、34、35、35:1、36、36:1、37、37:1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、86、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、199、213、214等， C.I.顏料橙2、5、13、16、17:1、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、71、73等， C.I.顏料紅1、2、3、4、5、6、7、9、10、14、17、22、23、31、38、41、48:1、48:2、48:3、48:4、49、49:1、49:2、52:1、52:2、53:1、57:1、60:1、63:1、66、67、81:1、81:2、81:3、83、88、90、105、112、119、122、123、144、146、149、150、155、166、168、169、170、171、172、175、176、177、178、179、184、185、187、188、190、200、202、206、207、208、209、210、216、220、224、226、242、246、254、255、264、270、272、279 C.I.顏料綠7、10、36、37、58、59 C.I.顏料紫1、19、23、27、32、37、42 C.I.顏料藍1、2、15、15:1、15:2、15:3、15:4、15:6、16、22、60、64、66、79、80 C.I.顏料黑1 該些有機顏料能夠單獨使用，或者為了提高色彩純度而組合使用各種顏料。The following are mentioned as an organic pigment. However, the present invention is not limited to these. CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36 , 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97 , 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139 , 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179 , 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc., CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46 , 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc., CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17 , 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57 : 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279 CI Pigment Green 7, 10, 36, 37, 58, 59 CI Pigment Violet 1, 19, 23, 27, 32, 37, 42 CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80 CI Pigment Black 1 These organic pigments can be used singly or in combination to improve color purity.

作為染料能夠使用例如在日本特開昭64-90403號公報、日本特開昭64-91102號公報、日本特開平1-94301號公報、日本特開平6-11614號公報、日本專利第2592207號公報、美國專利4808501號說明書、美國專利5667920號說明書、美國專利505950號說明書、美國專利5667920號說明書、日本特開平5-333207號公報、日本特開平6-35183號公報、日本特開平6-51115號公報、日本特開平6-194828號公報等中公開之色素。若作為化學結構而區分，能夠使用吡唑偶氮化合物、吡咯亞甲基化合物、苯胺基偶氮化合物、三苯基甲烷化合物、蒽醌化合物、亞芐基化合物、氧雜菁化合物、吡唑并***偶氮化合物、吡啶酮偶氮化合物、花青化合物、啡噻嗪化合物、吡咯并吡唑偶氮次甲基（pyrrolo pyrazole azomethine）化合物等。又，作為染料亦可以使用色素多聚物。作為色素多聚物，可以舉出在日本特開2011-213925號公報、日本特開2013-041097號公報中記載之化合物。For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, and JP-A No. 2592207 , U.S. Patent No. 4,808, 051, U.S. Patent No. 5, 568, 920, U.S. Patent No. 5, 560, 950, U.S. Patent No. 5, 595, 950, U.S. Patent No. 5,567, 920, Japanese Patent Application Laid-Open No. Hei No. Hei No. 5-333207, Japanese Patent Laid-Open No. Hei 6-35183, No. 6-51115 The pigment disclosed in Japanese Laid-Open Patent Publication No. Hei 6-194928 or the like. If it is distinguished as a chemical structure, a pyrazole azo compound, a pyrrolemethylene compound, an anilino azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, an oxophthalocyanine compound, or a pyrazole can be used. A triazole azo compound, a pyridone azo compound, a cyanine compound, a phenothiazine compound, a pyrrolopyrazole azomethine compound, or the like. Further, a dye polymer can also be used as the dye. The compound described in JP-A-2011-213925, and JP-A-2013-041097 can be mentioned as a pigment.

又，其他著色劑還能夠使用日本特開2013-41097號公報的段落號0084～0134的記載以及日本特開2011-162760號公報的段落號0029～0136的記載之偶氮色素。In addition, as the other coloring agent, the azo dye described in paragraphs 0084 to 0134 of JP-A-2013-41097 and paragraphs 0029 to 0136 of JP-A-2011-162760 can be used.

本發明的著色組成物中，其他著色劑的含量相對於著色劑的總量為1～30質量%為較佳。上限為25質量%以下為更佳，20質量%以下為進一步較佳，15質量%以下為更進一步較佳。下限為3質量%以上為更佳，5質量%以上為進一步較佳，7質量%以上為更進一步較佳。 又，還能夠設為實質上不含有其他著色劑之態樣。另外，所謂實質上不含有其他著色劑係指，例如相對於著色劑的總量為0.1質量%以下為較佳，0.05質量%以下為更佳，不含有為進一步較佳。In the coloring composition of the present invention, the content of the other coloring agent is preferably from 1 to 30% by mass based on the total amount of the coloring agent. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less. The lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more. Further, it is also possible to set a state in which substantially no other coloring agent is contained. In addition, it is preferable that the total amount of the coloring agent is not more than 0.1% by mass or less, more preferably 0.05% by mass or less, and even more preferably.

本發明的著色組成物中，著色劑的含量相對於著色組成物中的總固體成分為10～60質量%為較佳。下限為20質量%以上為更佳，30質量%以上為進一步較佳。上限為55質量%以下為更佳。只要著色劑的含量為上述範圍，便能夠提高除著色劑以外的成分的含量，能夠更加提高顯影性。In the colored composition of the present invention, the content of the colorant is preferably from 10 to 60% by mass based on the total solid content of the coloring composition. The lower limit is preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 55% by mass or less. When the content of the colorant is in the above range, the content of components other than the colorant can be increased, and the developability can be further improved.

＜＜硬化性化合物＞＞ 本發明的著色組成物含有硬化性化合物。作為硬化性化合物，能夠使用能夠藉由自由基、酸、熱進行交聯之公知的化合物。 在本發明中，硬化性化合物例如可以舉出含有具有乙烯性不飽和键之基團、環狀醚（環氧、氧雜環丁烷）基、羥甲基等之化合物，具有乙烯性不飽和键之化合物為較佳。作為具有乙烯性不飽和键之基團，可以舉出乙烯基、（甲基）烯丙基、（甲基）丙烯醯基等。 在本發明中，硬化性化合物為能夠藉由自由基進行聚合之化合物為較佳，自由基聚合性化合物為較佳，光自由基聚合性化合物（以下，將自由基聚合性化合物亦稱作聚合性化合物）為更佳。<<Curable Compound>> The colored composition of the present invention contains a curable compound. As the curable compound, a known compound which can be crosslinked by a radical, an acid or heat can be used. In the present invention, the curable compound may, for example, be a compound containing a group having an ethylenically unsaturated bond, a cyclic ether (epoxy group, oxetane) group, or a methylol group, and has an ethylenic unsaturated property. The compound of the bond is preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryl fluorenyl group. In the present invention, the curable compound is preferably a compound which can be polymerized by a radical, and a radically polymerizable compound is preferable, and a photoradical polymerizable compound (hereinafter, a radically polymerizable compound is also called polymerization). Sex compounds) are better.

聚合性化合物例如可以為單體、預聚物、亦即可以為二聚物、三聚物以及寡聚物或該些混合物以及該些多聚物等化學形態中的任一個。聚合性化合物為單體為較佳。 聚合性化合物為3～15官能的（甲基）丙烯酸酯化合物為較佳，3～6官能的（甲基）丙烯酸酯化合物為更佳。 聚合性化合物的分子量為100～3000為較佳，200～2000為更佳。 作為單體、預聚物的例子，可以舉出不飽和羧酸（例如丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、異巴豆酸、馬來酸等）或其酯類、醯胺類以及該等之多聚物，較佳為不飽和羧酸和脂肪族多元醇化合物之酯、不飽和羧酸和脂肪族多元胺化合物之醯胺類、以及該等之多聚物。又，亦可適宜地使用具有羥基、氨基、巰基等親核性取代基之不飽和羧酸酯或醯胺類與單官能或者多官能異氰酸酯類或環氧類之加成反應物，以及與單官能或者多官能的羧酸之脱水縮合反應物等。又，亦可適宜地使用具有異氰酸酯基、環氧基等親電子性取代基之不飽和羧酸酯或醯胺類與單官能或者多官能的醇類、胺類、硫醇類之反應物，以及具有鹵素基、甲苯磺醯氧基等脱離性取代基之不飽和羧酸酯或醯胺類與單官能或者多官能的醇類、胺類、硫醇類之反應物。又，亦可使用將上述不飽和羧酸取代為不飽和膦酸、苯乙烯等乙烯基苯衍生物、乙烯基醚、烯丙基醚等之化合物組。 作為該些具體的化合物，亦可將在日本特開2009-288705號公報的段落號0095～0108中記載之化合物適宜地使用於本發明中。The polymerizable compound may be, for example, a monomer, a prepolymer, or any of a chemical form such as a dimer, a trimer, or an oligomer, or a mixture thereof, or a plurality of such polymers. The polymerizable compound is preferably a monomer. The polymerizable compound is preferably a 3- to 15-functional (meth) acrylate compound, and more preferably a 3- to 6-functional (meth) acrylate compound. The molecular weight of the polymerizable compound is preferably from 100 to 3,000, more preferably from 200 to 2,000. Examples of the monomer and the prepolymer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, guanamines, and the like. Such polymers are preferably esters of unsaturated carboxylic acids and aliphatic polyol compounds, amides of unsaturated carboxylic acids and aliphatic polyamine compounds, and such polymers. Further, an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amino group or a fluorenyl group, or an addition reaction product of a monofunctional or polyfunctional isocyanate or an epoxy group, and a single compound may be suitably used. A dehydration condensation reaction of a functional or polyfunctional carboxylic acid or the like. Further, a reaction product of an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or a guanamine and a monofunctional or polyfunctional alcohol, an amine or a thiol may be suitably used. And a reaction product of an unsaturated carboxylic acid ester or a guanamine having a destructive substituent such as a halogen group or a tosyloxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, a compound group obtained by substituting the above unsaturated carboxylic acid with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether or an allyl ether may be used. As the specific compound, the compound described in paragraphs 0095 to 0108 of JP-A-2009-288705 can be suitably used in the present invention.

在本發明中，作為聚合性化合物，含有1個以上具有乙烯性不飽和鍵之基團、且在常壓下具有100℃以上的沸點之化合物亦為較佳。作為其例子，例如可以參閱在日本特開2013-29760號公報的段落號0227、日本特開2008-292970號公報的段落號0254～0257中記載之化合物，並將該內容編入本申請說明書中。In the present invention, a compound having one or more groups having an ethylenically unsaturated bond and having a boiling point of 100 ° C or higher at normal pressure is also preferable as the polymerizable compound. For example, the compound described in paragraphs 0227 to 0257 of JP-A-2013-29760, and JP-A-2008-292970, and the contents of the contents of the present application are incorporated herein by reference.

聚合性化合物較佳為二季戊四醇三丙烯酸酯（市售品為KAYARAD D-330；NIPPON KAYAKU CO.,LTD.製造）、二季戊四醇四丙烯酸酯（市售品為KAYARAD D-320；NIPPON KAYAKU CO.,LTD.製造）、二季戊四醇五（甲基）丙烯酸酯（市售品為KAYARAD D-310；NIPPON KAYAKU CO.,LTD.製造）、二季戊四醇六（甲基）丙烯酸酯（市售品為KAYARAD DPHA；NIPPON KAYAKU CO.,LTD.製造、NK酯A-DPH-12E；SHIN-NAKAMURA CHEMICAL CO.,LTD.製造）、以及該等之（甲基）丙烯醯基經由乙二醇、丙二醇殘基之結構（例如由SARTOMER Company,Inc.市售之SR454、SR499）。亦可以使用該等的寡聚物類型。又，亦可使用KAYARAD RP-1040（NIPPON KAYAKU CO.,LTD.製造）、NK酯A-TMMT（SHIN-NAKAMURA CHEMICAL CO.,LTD.製造）。 以下表示較佳的聚合性化合物的態樣。The polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by NIPPON KAYAKU CO., LTD.) or dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; NIPPON KAYAKU CO.). , manufactured by LTD.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by NIPPON KAYAKU CO., LTD.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD) DPHA; manufactured by NIPPON KAYAKU CO., LTD., NK ester A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), and these (meth)acrylonyl groups via ethylene glycol, propylene glycol residues The structure (for example, SR454, SR499, marketed by SARTOMER Company, Inc.). These types of oligomers can also be used. Further, KAYARAD RP-1040 (manufactured by NIPPON KAYAKU CO., LTD.) or NK ester A-TMMT (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.) can also be used. The aspect of the preferred polymerizable compound is shown below.

聚合性化合物可以具有羧基、磺酸基、磷酸基等酸基。作為具有酸基之聚合性化合物，脂肪族多羥基化合物與不飽和羧酸的酯為較佳，使非芳香族羧酸酐與脂肪族多羥基化合物的未反應的羥基反應而具有酸基之聚合性化合物為更佳，該酯中脂肪族多羥基化合物為季戊四醇和/或二季戊四醇者為特佳。作為市售品，例如可以舉出TOAGOSEI CO.,LTD.製造的多元酸改質丙烯酸寡聚物，亦即ARONIX M-510、ARONIX M-520、ARONIX TO-2349等。The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a non-aromatic carboxylic anhydride is reacted with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to have an acid group polymerizability. More preferably, the compound is particularly preferred in the case where the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. The commercially available product may, for example, be a polybasic acid-modified acrylic oligomer manufactured by TOAGOSEI CO., LTD., that is, ARONIX M-510, ARONIX M-520, ARONIX TO-2349, or the like.

作為具有酸基之聚合性化合物的酸值，0.1～40mgKOH/g為較佳，5～30mgKOH/g為特佳。若聚合性化合物的酸值為0.1mgKOH/g以上，則顯影溶解特性良好，若為40mgKOH/g以下，則在製造和處理上有利。進而，光聚合性能良好且硬化性優異。The acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH/g, and particularly preferably from 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development and dissolution characteristics are good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling. Further, the photopolymerization performance is good and the curability is excellent.

聚合性化合物中具有己內酯結構之化合物亦為較佳態樣。 作為具有己內酯結構之化合物，只要在分子內具有己內酯結構則無特別的限定，例如可以舉出ε-己內酯改質多官能（甲基）丙烯酸酯，該ε-己內酯改質多官能（甲基）丙烯酸酯可以藉由將三羥甲基乙烷、二-三羥甲基乙烷、三羥甲基丙烷、二-三羥甲基丙烷、季戊四醇、二季戊四醇、三季戊四醇、甘油、二甘油、三羥甲基三聚氰胺等多元醇與（甲基）丙烯酸以及ε-己內酯加以酯化而得到。其中，具有由下述通式（Z-1）表示之己內酯結構之化合物為較佳。A compound having a caprolactone structure among the polymerizable compounds is also preferred. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include ε-caprolactone-modified polyfunctional (meth)acrylate, and the ε-caprolactone. The modified polyfunctional (meth) acrylate can be obtained by using trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, three Polyols such as pentaerythritol, glycerin, diglycerin, and trimethylol melamine are obtained by esterification with (meth)acrylic acid and ε-caprolactone. Among them, a compound having a caprolactone structure represented by the following formula (Z-1) is preferred.

【化學式39】 [Chemical Formula 39]

在通式（Z-1）中，6個R全部為由下述通式（Z-2）表示之基團，或者6個R中的1～5個為由下述通式（Z-2）表示之基團，其餘為由下述通式（Z-3）表示之基團。In the general formula (Z-1), all of the six R's are represented by the following formula (Z-2), or one to five of the six R are represented by the following formula (Z-2) The group represented by the formula is the group represented by the following formula (Z-3).

【化學式40】 [Chemical Formula 40]

在通式（Z-2）中，R1 表示氫原子或甲基，m表示1或2的數，“*”表示鍵結鍵。In the formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond.

【化學式41】 [Chemical Formula 41]

在通式（Z-3）中，R1 表示氫原子或甲基，“*”表示鍵結鍵。In the formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "*" represents a bond.

具有己內酯結構之聚合性化合物例如由NIPPON KAYAKU CO., LTD.作為KAYARAD DPCA系列而市售，可以舉出DPCA-20（上述式（Z-1）～（Z-3）中，m=1、由式（Z-2）表示之基團的個數=2、R1 全部為氫原子之化合物）、DPCA-30（上述式（Z-1）～（Z-3）中，m=1、由式（Z-2）表示之基團的個數=3、R1 全部為氫原子之化合物）、DPCA-60（上述式（Z-1）～（Z-3）中，m=1、由式（Z-2）表示之基團的個數=6、R1 全部為氫原子之化合物）、DPCA-120（上述式（Z-1）～（Z-3）中，m=2、由式（Z-2）表示之基團的個數=6、R1 全部為氫原子之化合物）等。A polymerizable compound having a caprolactone structure is commercially available, for example, from NIPPON KAYAKU CO., LTD. as KAYARAD DPCA series, and DPCA-20 (in the above formulas (Z-1) to (Z-3), m= 1. The number of groups represented by the formula (Z-2) = 2, the compound in which all R 1 are hydrogen atoms), DPCA-30 (in the above formula (Z-1) to (Z-3), m = 1. The number of groups represented by the formula (Z-2) = 3, the compound in which all R 1 are a hydrogen atom), and DPCA-60 (in the above formula (Z-1) to (Z-3), m = 1. The number of groups represented by the formula (Z-2) = 6, the compound in which all of R 1 is a hydrogen atom), DPCA-120 (in the above formula (Z-1) to (Z-3), m = 2. A compound represented by the formula (Z-2) = 6, a compound in which all R 1 are a hydrogen atom).

聚合性化合物可以使用由下述通式（Z-4）或（Z-5）表示之化合物。As the polymerizable compound, a compound represented by the following formula (Z-4) or (Z-5) can be used.

【化學式42】 [Chemical Formula 42]

在通式（Z-4）以及（Z-5）中，E分別獨立地表示-（（CH2 ）y CH2 O）-或-（（CH2 ）y CH（CH3 ）O）-，y分別獨立地表示0～10的整數，X分別獨立地表示（甲基）丙烯醯基、氫原子或羧基。 在通式（Z-4）中，（甲基）丙烯醯基的合計為3個或4個，m分別獨立地表示0～10的整數，各m的合計為0～40的整數。 在通式（Z-5）中，（甲基）丙烯醯基的合計為5個或6個，n分別獨立地表示0～10的整數，各n的合計為0～60的整數。In the general formulae (Z-4) and (Z-5), E independently represents -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)-, y each independently represents an integer of 0 to 10, and X each independently represents a (meth)acryloyl group, a hydrogen atom or a carboxyl group. In the general formula (Z-4), the total of (meth)acrylonyl groups is three or four, and m each independently represents an integer of from 0 to 10, and the total of each m is an integer of from 0 to 40. In the general formula (Z-5), the total of (meth)acrylonyl groups is 5 or 6, and n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

在通式（Z-4）中，m為0～6的整數為較佳，0～4的整數為更佳。 又，各m的合計為2～40的整數為較佳，2～16的整數為更佳，4～8的整數為特佳。 在通式（Z-5）中，n為0～6的整數為較佳，0～4的整數為更佳。 又，各n的合計為3～60的整數為較佳，3～24的整數為更佳，6～12的整數為特佳。 又，在通式（Z-4）或通式（Z-5）中的-（（CH2 ）y CH2 O）-或-（（CH2 ）y CH（CH3 ）O）-較佳為氧原子側的末端與X鍵結之形態。In the general formula (Z-4), m is preferably an integer of 0 to 6, and an integer of 0 to 4 is more preferably. Further, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and an integer of 4 to 8 is particularly preferable. In the general formula (Z-5), n is an integer of 0 to 6 and preferably an integer of 0 to 4 is more preferable. Further, the total of n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and an integer of 6 to 12 is particularly preferable. Further, -((CH 2 ) y CH 2 O)- or -((CH 2 ) y CH(CH 3 )O)- in the formula (Z-4) or the formula (Z-5) is preferred. It is a form in which the end of the oxygen atom side is bonded to X.

由通式（Z-4）或通式（Z-5）表示之化合物可以單獨使用1種，亦可倂用2種以上。在通式（Z-5）中，6個X全部為丙烯醯基之形態為特佳。The compound represented by the formula (Z-4) or the formula (Z-5) may be used singly or in combination of two or more. In the general formula (Z-5), the form in which all six X are acrylonitrile groups is particularly preferable.

又，作為由通式（Z-4）或通式（Z-5）表示之化合物的聚合性化合物中之總含量，20質量%以上為較佳、50質量%以上為更佳。In addition, the total content of the polymerizable compound of the compound represented by the formula (Z-4) or the formula (Z-5) is preferably 20% by mass or more, more preferably 50% by mass or more.

由通式（Z-4）或通式（Z-5）表示之化合物能夠藉由以下以往公知的製程而合成：藉由開環加成反應使環氧乙烷或環氧丙烷的開環骨架鍵結於季戊四醇或二季戊四醇之製程；以及例如使（甲基）丙烯醯氯與開環骨架的末端羥基反應而導入（甲基）丙烯醯基之製程。各製程為被廣為人知之製程，本領域技術人員能夠容易地合成由通式（Z-4）或（Z-5）表示之化合物。The compound represented by the formula (Z-4) or the formula (Z-5) can be synthesized by a conventionally known process: a ring-opening skeleton of ethylene oxide or propylene oxide by a ring-opening addition reaction The process of bonding to pentaerythritol or dipentaerythritol; and, for example, a process of reacting (meth)acrylofluorene chloride with a terminal hydroxyl group of a ring-opening skeleton to introduce a (meth)acrylonitrile group. Each process is a well-known process, and those skilled in the art can easily synthesize a compound represented by the formula (Z-4) or (Z-5).

由通式（Z-4）或通式（Z-5）表示之化合物中，季戊四醇衍生物和/或二季戊四醇衍生物為更佳。 具體而言，可以舉出由下述式（a）～（f）表示之化合物（以下亦稱作“例示化合物（a）～（f）”。），其中，例示化合物（a）、（b）、（e）、（f）為較佳。Among the compounds represented by the formula (Z-4) or the formula (Z-5), a pentaerythritol derivative and/or a dipentaerythritol derivative are more preferable. Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to (f)"), wherein the compounds (a) and (b) are exemplified. ), (e), (f) are preferred.

【化學式43】 [Chemical Formula 43]

【化學式44】 [Chemical Formula 44]

作為由通式（Z-4）、（Z-5）表示之聚合性化合物的市售品，例如可以舉出SARTOMER Company,Inc.製造之具有4個乙烯氧基鏈之4官能丙烯酸酯之SR-494，NIPPON KAYAKU CO.,LTD.製造之具有6個戊二烯氧基鏈之6官能丙烯酸酯之DPCA-60、具有3個異丁烯氧基鏈之3官能丙烯酸酯之TPA-330等。As a commercial item of the polymerizable compound represented by the general formula (Z-4) or (Z-5), for example, SR of a tetrafunctional acrylate having four ethyleneoxy chains manufactured by SARTOMER Company, Inc. -494, DPCA-60 of 6-functional acrylate having 6 pentadienyloxy chains, TPA-330 having 3 functional acrylates of isobutyleneoxy chain, and the like, manufactured by NIPPON KAYAKU CO., LTD.

作為聚合性化合物，如日本特公昭48-41708號公報、日本特開昭51-37193號公報、日本特公平2-32293號公報、日本特公平2-16765號公報中記載之氨酯丙烯酸酯類，日本特公昭58-49860號公報、日本特公昭56-17654號公報、日本特公昭62-39417號公報、日本特公昭62-39418號公報中記載之具有環氧乙烷系骨架之氨酯化合物類亦適宜。又，藉由使用日本特開昭63-277653號公報、日本特開昭63-260909號公報、日本特開平1-105238號公報中記載之、在分子內具有氨基結構和硫化物結構之加成聚合性化合物類，能夠得到感光速度非常優異之著色組成物。 作為市售品，可以舉出氨酯寡聚物UAS-10、UAB-140（SANYO-KOKUSAKU PULP CO.,LTD.製造）、UA-7200（SHIN-NAKAMURA CHEMICAL CO.,LTD.製造）、DPHA-40H（NIPPON KAYAKU CO.,LTD.製造）、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600（KYOEISHA CHEMICAL CO.,LTD.製造）等。The urethane acrylates described in Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. A urethane compound having an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho 62-49860, Japanese Patent Publication No. Sho 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 The class is also suitable. In addition, the addition of an amino group structure and a sulfide structure in the molecule is described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A polymerizable compound can provide a coloring composition which is excellent in the photosensitivity. The commercially available product is urethane oligomer UAS-10, UAB-140 (made by SANYO-KOKUSAKU PULP CO., LTD.), UA-7200 (made by SHIN-NAKAMURA CHEMICAL CO., LTD.), DPHA. -40H (manufactured by NIPPON KAYAKU CO., LTD.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by KYOEISHA CHEMICAL CO., LTD.).

在本發明的著色組成物中，硬化性化合物相對於著色組成物的總固體成分之含量為0.1～40質量%為較佳。下限例如為0.5質量%以上為更佳，1質量%以上為進一步較佳。上限例如為30質量%以下為更佳，20質量%以下為進一步較佳。 硬化性化合物可以單獨使用1種，亦可倂用2種以上。在倂用2種以上之情況下，總量成為上述範圍為較佳。In the colored composition of the present invention, the content of the curable compound relative to the total solid content of the colored composition is preferably from 0.1 to 40% by mass. The lower limit is, for example, 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is, for example, preferably 30% by mass or less, more preferably 20% by mass or less. The curable compound may be used singly or in combination of two or more. When two or more types are used, the total amount is preferably in the above range.

＜＜多官能硫醇化合物＞＞ 本發明的著色組成物以促進聚合性化合物的反應等為目的，可以含有在分子內具有2個以上的巰基之多官能硫醇化合物。多官能硫醇化合物為二級烷烴硫醇類為較佳，係具有由下述通式（T1）表示之結構之化合物為特佳。 通式（T1） 【化學式45】（在式（T1）中，n表示2～4的整數，L表示2～4價的連接基團。）<<Polyfunctional thiol compound>> The colored composition of the present invention may contain a polyfunctional thiol compound having two or more fluorenyl groups in the molecule for the purpose of promoting the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkane thiol, and is preferably a compound having a structure represented by the following formula (T1). General formula (T1) [Chemical Formula 45] (In the formula (T1), n represents an integer of 2 to 4, and L represents a linking group of 2 to 4 valence.)

在上述通式（T1）中，連接基團L係碳原子數為2～12的脂肪族基團為較佳，n為2，L係碳原子數為2～12的伸烷基為特佳。多官能硫醇化合物的具體例可以舉出由下述結構式（T2）～（T4）表示之化合物，由式（T2）表示之化合物為特佳。該些多官能硫醇可以使用1種或組合複數種而使用。In the above formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, n is 2, and an L-alkyl group having 2 to 12 carbon atoms is particularly preferable. . Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulae (T2) to (T4), and the compound represented by the formula (T2) is particularly preferred. These polyfunctional thiols can be used singly or in combination of plural kinds.

【化學式46】 [Chemical Formula 46]

在本發明的著色組成物含有多官能硫醇的情況下，多官能硫醇的含量相對於著色組成物的總固體成分為0.3～8.9質量%為較佳，0.8～6.4質量%為更佳。又，多官能硫醇亦可作為改善穩定性、臭味、解析度、顯影性、密合性等的目的而添加。In the case where the colored composition of the present invention contains a polyfunctional thiol, the content of the polyfunctional thiol is preferably from 0.3 to 8.9% by mass, more preferably from 0.8 to 6.4% by mass, based on the total solid content of the colored composition. Further, the polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like.

＜＜光聚合起始劑＞＞ 本發明的著色組成物含有光聚合起始劑為較佳。 作為光聚合起始劑，只要具有引發聚合性化合物的聚合的能力，則無特別的限制，可以從公知的光聚合起始劑中適當地進行選擇。例如對紫外線區域至可見光線具有感光性者為較佳。又，可以是與被光激發之增感劑產生某些作用而生成活性自由基之活性劑，亦可以是根據單體的種類而引發陽離子聚合之起始劑。 又，光聚合起始劑至少含有1種在約300nm～800nm（330nm～500nm為更佳。）的範圍內至少具有約50莫耳吸光係數之化合物為較佳。<<Photopolymerization initiator>> The coloring composition of the invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferred that the ultraviolet region has a sensitivity to visible light. Further, it may be an active agent which generates a living radical by some action with a photo-stimulated sensitizer, or may be an initiator which initiates cationic polymerization depending on the kind of the monomer. Further, the photopolymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 moles in a range of from about 300 nm to 800 nm (more preferably from 330 nm to 500 nm).

作為光聚合起始劑，例如可以舉出鹵化烴衍生物（例如具有三嗪骨架者、具有噁二唑骨架者等）、醯基膦氧化物等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫代化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮等。作為具有三嗪骨架之鹵化烴化合物，例如可以舉出如下化合物等：若林等著、Bull.Chem.Soc.Japan，42、2924（1969）記載之化合物、英国專利1388492號說明書記載之化合物、日本特開昭53-133428號公報記載之化合物、德國專利3337024號說明書記載之化合物、基於F.C.Schaefer等之J. Org.Chem.；29、1527（1964）記載之化合物、日本特開昭62-58241號公報記載之化合物、日本特開平5-281728號公報記載之化合物、日本特開平5-34920號公報記載化合物、美國專利第4212976號說明書中記載之化合物。Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton or a oxadiazole skeleton), a mercaptophosphine compound such as a mercaptophosphine oxide, or a hexaarylbisimidazole or an anthracene. An anthracene compound such as a derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, or a hydroxyacetophenone. Examples of the halogenated hydrocarbon compound having a triazine skeleton include the following compounds, such as those described in Bull et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), and compounds described in British Patent No. 1,388,492. The compound described in JP-A-53-133428, the compound described in the specification of German Patent No. 3337024, and the compound described in J. Org. Chem.; 29, 1527 (1964) by FC Schaefer et al., JP-A-62-58241 The compound described in the Japanese Patent Publication No. Hei 5-281728, the compound described in JP-A-H05-34920, and the compound described in the specification of U.S. Patent No. 4,212,976.

又，從曝光感度的觀點來看，選自由三鹵甲基三嗪化合物、芐基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三烯丙基咪唑二聚物、鎓化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯-苯-鐵絡合物及其鹽、鹵甲基噁二唑化合物、經3-芳基取代的香豆素化合物構成之群之化合物為較佳。Further, from the viewpoint of exposure sensitivity, it is selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a mercaptophosphine compound, and a phosphine oxide compound. , metallocene compound, hydrazine compound, triallyl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex A compound of the group consisting of a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound is preferred.

三鹵甲基三嗪化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、肟化合物、三烯丙基咪唑二聚物、鎓化合物、二苯甲酮化合物、苯乙酮化合物為進一步較佳，選自由三鹵甲基三嗪化合物、α-胺基酮化合物、肟化合物、三烯丙基咪唑二聚物、二苯甲酮化合物構成之群之至少一種化合物為特佳。a trihalomethyltriazine compound, an α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a benzophenone compound, and an acetophenone compound are Further preferably, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a benzophenone compound is particularly preferred.

尤其，在製造固體攝像元件的彩色濾光片時使用本發明的著色組成物之情況下，由於需要以尖細形狀形成微細圖案，因此硬化性和對未曝光部無殘渣的方式進行顯影非常重要。從該種觀點來看，作為光聚合起始劑而使用肟化合物為特佳。尤其，在固體攝像元件中形成微細圖案之情況下，硬化用曝光中使用步進機曝光，但是該曝光機有時會因鹵素而損傷，還需要將光聚合起始劑的添加量抑制得較低，因此考慮到該點，在形成如固體攝像元件的微細圖案時，作為光聚合起始劑而使用肟化合物為特佳。又，藉由使用肟化合物而能夠更加優化移染性。 作為光聚合起始劑的具體例，例如可以參閱日本特開2013-29760號公報的段落號0265～0268，將該內容編入本申請說明書中。In particular, when the coloring composition of the present invention is used in the production of a color filter of a solid-state image sensor, since it is necessary to form a fine pattern in a tapered shape, it is important to develop the hardenability and the manner in which no residue is formed in the unexposed portion. . From such a viewpoint, it is particularly preferable to use a ruthenium compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state image sensor, exposure by a stepper is used for exposure for curing, but the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator. In view of this, in the case of forming a fine pattern such as a solid-state image sensor, it is particularly preferable to use a ruthenium compound as a photopolymerization initiator. Moreover, the transferability can be further optimized by using a ruthenium compound. As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP-A-2013-29760 can be referred to, and the contents are incorporated in the specification of the present application.

作為光聚合起始劑，亦能夠適宜地使用羥基苯乙酮化合物、胺基苯乙酮化合物以及醯基膦化合物。更具體而言，例如亦可以使用日本特開平10-291969號公報中記載之胺基苯乙酮系起始劑、專利第4225898號公報中記載之醯基膦系起始劑。 作為羥基苯乙酮系起始劑，可以使用IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959，IRGACURE-127（商品名稱：均為BASF公司製造）。 作為胺基苯乙酮系起始劑，可以使用作為市售品之IRGACURE-907、IRGACURE-369以及IRGACURE-379EG（商品名稱：均為BASF公司製造）。胺基苯乙酮系起始劑亦可使用吸收波長與365nm或405nm等長波光源匹配之日本特開2009-191179公報中記載之化合物。 作為醯基膦系起始劑，可以使用市售品之IRGACURE-819、DAROCUR-TPO（商品名稱：均為BASF公司製造）。As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and a mercaptophosphine-based initiator described in Patent No. 4,258,899 can be used. As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade name: all manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF Corporation) which are commercially available can be used. The amine acetophenone-based initiator may also be a compound described in JP-A-2009-191179, which has an absorption wavelength matched with a long-wavelength light source such as 365 nm or 405 nm. As the mercaptophosphine-based initiator, commercially available products IRGACURE-819 and DAROCUR-TPO (trade names: all manufactured by BASF Corporation) can be used.

作為光聚合起始劑，可以更為較佳地舉出肟化合物。 作為肟化合物的具體例，可以使用日本特開2001-233842號公報記載之化合物、日本特開2000-80068號公報記載之化合物、日本特開2006-342166號公報記載之化合物。 作為能夠適宜地使用於本發明之肟化合物，例如可以舉出3-苯甲醯氧基亞胺基丁烷-2-酮、3-乙醯氧基亞胺基丁烷-2-酮、3-丙醯氧基亞胺基丁烷-2-酮、2-乙醯氧基亞胺基戊烷-3-酮、2-乙醯氧基亞胺基-1-苯基丙烷-1-酮、2-苯甲醯氧基亞胺基-1-苯基丙烷-1-酮、3-（4-甲苯磺醯氧基）亞胺基丁烷-2酮以及2-乙氧基羰氧基亞胺基-1-苯基丙烷-1-酮等。 又，亦可以舉出J.C.S.Perkin II（1979年）pp.1653-1660、J.C.S.Perkin II（1979年）pp.156-162、Journal of Photopolymer Science and Technology（1995年）pp.202-232、日本特開2000-66385號公報記載之化合物、日本特開2000-80068號公報、日本專利公表2004-534797號公報、日本特開2006-342166號公報等各公報中記載之化合物等。 市售品中，亦可適宜地使用IRGACURE-OXE01（BASF公司製造）、IRGACURE-OXE02（BASF公司製造）。又，亦可使用TR-PBG-304（常州強力電子新材料有限公司製造）、ADEKA ARKLS NCI-831以及ADEKA ARKLS NCI-930（ADEKA CORPORATION製造）。As the photopolymerization initiator, a ruthenium compound can be more preferably mentioned. As a specific example of the ruthenium compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used. Examples of the ruthenium compound which can be suitably used in the present invention include 3-benzylideneoxyimidobutan-2-one and 3-ethyloxyiminobutan-2-one, and 3 - propionyloxyiminobutan-2-one, 2-ethoxymethoxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropan-1-one , 2-benzylideneoxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2one, and 2-ethoxycarbonyloxyl Imino-1-phenylpropan-1-one and the like. Further, JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, and Japanese specials are also cited. The compound described in each of the publications such as JP-A-2000-80068, JP-A-2000-80068, and JP-A-2006-342166, and JP-A-2006-342166. In the commercial product, IRGACURE-OXE01 (manufactured by BASF Corporation) and IRGACURE-OXE02 (manufactured by BASF Corporation) can also be suitably used. Further, TR-PBG-304 (manufactured by Changzhou Strong Electronic New Material Co., Ltd.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used.

又，作為上述記載以外的肟化合物，亦可使用肟連接於咔唑N位之日本專利公表2009-519904號公報中記載之化合物、在二苯甲酮部位導入有雜取代基之美國專利第7626957號說明書中記載之化合物、在色素部位導入有硝基之日本特開2010-15025號公報以及美國專利特開2009-292039號說明書中記載之化合物、国際公開專利2009-131189號公報中記載之酮肟化合物、在同一分子內含有三嗪骨架和肟骨架之在美國專利7556910號說明書中記載之化合物、在405nm具有最大吸收，且對g線光源具有良好的感度之日本特開2009-221114號公報記載之化合物等。 較佳為例如可以參閱日本特開2013-29760號公報的段落號0274～0275，將該內容編入本申請說明書中。 具體而言，作為肟化合物，由下述式（OX-1）表示之化合物為較佳。另外，肟的N-O鍵可以為（E）體的肟化合物，亦可以為（Z）體的肟化合物，亦可以為（E）體與（Z）體的混合物。In addition, as the ruthenium compound other than the above-mentioned, a compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is attached to the N-position of the carbazole, and a U.S. Patent No. 7,626,957 to which a hetero substituent is introduced at the benzophenone site can be used. The compound described in the specification, the compound described in the specification of the Japanese Patent Laid-Open Publication No. 2010-15025, and the ketone described in the specification of the International Patent Publication No. 2009-131189. The ruthenium compound, the compound described in the specification of U.S. Patent No. 7,569,910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has a maximum absorption at 405 nm, and has a good sensitivity to a g-line light source, and Japanese Laid-Open Patent Publication No. 2009-221114 The compound or the like described. For example, it is preferable to refer to paragraphs 0274 to 0275 of JP-A-2013-29760, and the contents are incorporated in the specification of the present application. Specifically, as the hydrazine compound, a compound represented by the following formula (OX-1) is preferred. Further, the N-O bond of ruthenium may be an oxime compound of the (E) form, a ruthenium compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

【化學式47】 [Chemical Formula 47]

在通式（OX-1）中，R以及B分別獨立地表示一價取代基，A表示二價有機基，Ar表示芳基。 在通式（OX-1）中，作為由R表示之一價取代基，一價非金屬原子團為較佳。 作為一價的非金屬原子團，可以舉出烷基、芳基、醯基、烷氧基羰基、芳氧基羰基、雜環基、烷硫基羰基、芳硫基羰基等。又，該些基團亦可具有1個以上的取代基。又，前述取代基亦可以進一步被其他取代基取代。 作為取代基，可以舉出鹵素原子、芳氧基、烷氧基羰基或芳氧基羰基、醯氧基、醯基、烷基、芳基等。 在通式（OX-1）中，作為由B表示之一價取代基，芳基、雜環基、芳基羰基或雜環羰基為較佳。該些基團亦可以具有1個以上的取代基。作為取代基，可例示前述取代基。 在通式（OX-1）中，作為由A表示之二價有機基，碳原子數為1～12的伸烷基、環伸烷基、伸炔基為較佳。該些基團亦可以具有1個以上的取代基。作為取代基，能夠例示前述取代基。In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. In the general formula (OX-1), as the monovalent substituent represented by R, a monovalent non-metal atomic group is preferred. The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the above substituent may be further substituted with another substituent. The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group. In the formula (OX-1), as the monovalent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have one or more substituents. The substituent may be exemplified as the substituent. In the formula (OX-1), as the divalent organic group represented by A, an alkylene group having a carbon number of 1 to 12, a cycloalkyl group or an alkynylene group is preferred. These groups may have one or more substituents. The substituent may be exemplified as the substituent.

本發明亦能夠使用具有氟原子之肟化合物作為光聚合起始劑。作為具有氟原子之肟化合物的具體例，可以舉出日本特開2010-262028號公報記載之化合物、日本專利公表2014-500852號公報記載之化合物24、36～40、日本特開2013-164471號公報記載之化合物（C-3）等。該內容編入本說明書中。The present invention can also use a ruthenium compound having a fluorine atom as a photopolymerization initiator. Specific examples of the ruthenium compound having a fluorine atom include the compounds described in JP-A-2010-262028, and the compounds 24 and 36-40 described in JP-A-2014-500852, and JP-A-2013-164471 Compound (C-3) or the like described in the publication. This content is incorporated in this specification.

本發明還能夠使用由下述通式（1）或（2）表示之化合物作為光聚合起始劑。 【化學式48】 The present invention can also use a compound represented by the following formula (1) or (2) as a photopolymerization initiator. [Chemical Formula 48]

式（1）中，R1 以及R2 分別獨立地表示碳原子數1～20的烷基、碳原子數4～20的脂環式烴基、碳原子數6～30的芳基或碳原子數7～30的芳烷基，在R1 以及R2 為苯基的情況下，苯基彼此可以鍵結而形成茀基，R3 以及R4 分別獨立地表示氫原子、碳原子數1～20的烷基、碳原子數6～30的芳基、碳原子數7～30的芳烷基或碳原子數4～20的雜環基，X表示直接鍵或羰基。In the formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or a carbon number. In the case of 7 to 30 aralkyl groups, when R 1 and R 2 are a phenyl group, the phenyl groups may be bonded to each other to form a fluorenyl group, and R 3 and R 4 each independently represent a hydrogen atom and have 1 to 20 carbon atoms. The alkyl group, the aryl group having 6 to 30 carbon atoms, the aralkyl group having 7 to 30 carbon atoms or the heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

式（2）中，R1 、R2 、R3 以及R4 的含義與式（1）中的R1 、R2 、R3 以及R4 相同，R5 表示-R6 、-OR6 、-SR6 、-COR6 、-CONR6 R6 、-NR6 COR6 、-OCOR6 、-COOR6 、-SCOR6 、-OCSR6 、-COSR6 、-CSOR6 、-CN、鹵素原子或羥基，R6 表示碳原子數1～20的烷基、碳原子數6～30的芳基、碳原子數7～30的芳烷基或碳原子數4～20的雜環基，X表示直接鍵或羰基，a表示0～4的整數。 (2), R 1, 1, R 2 , R 3 , and R is the same formula R 2, R 3 and R meanings formula R (1) 4 of 4, R 5 represents -R 6, -OR 6, -SR 6 , -COR 6 , -CONR 6 R 6 , -NR 6 COR 6 , -OCOR 6 , -COOR 6 , -SCOR 6 , -OCSR 6 , -COSR 6 , -CSOR 6 , -CN, halogen atom or The hydroxyl group, R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct A bond or a carbonyl group, and a represents an integer of 0-4.

上述式（1）以及式（2）中，R1 以及R2 分別獨立地為甲基、乙基、正丙基、異丙基、環己基或苯基為較佳。R3 為甲基、乙基、苯基、甲苯基或二甲苯基為較佳。R4 為碳原子數1～6的烷基或苯基為較佳。R5 為甲基、乙基、苯基、甲苯基或萘基為較佳。X為直接鍵為較佳。 作為由式（1）以及式（2）表示之化合物的具體例，例如可以舉出日本特開2014-137466號公報的段落號0076～0079中記載之化合物。該內容編入本說明書中。In the above formulas (1) and (2), R 1 and R 2 are each independently a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclohexyl group or a phenyl group. R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. It is preferred that X is a direct bond. Specific examples of the compound represented by the formula (1) and the formula (2) include the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated in this specification.

以下，示出在本發明中較佳地使用之肟化合物的具體例，但本發明係不限定於該些者。 【化學式49】 Specific examples of the ruthenium compound which is preferably used in the present invention are shown below, but the present invention is not limited thereto. [Chemical Formula 49]

肟化合物為在350nm～500nm的波長區域具有最大吸收波長者為較佳，在360nm～480nm的波長區域具有吸收波長者為更佳，365nm以及405nm的吸光度較高者為特佳。 肟化合物中，從感度的觀點來看，365nm或405nm中之莫耳吸光係數為1,000～300,000為較佳，2,000～300,000為更佳，5,000～200,000為特佳。 化合物的莫耳吸光係數可使用公知的方法，例如使用紫外可見分光光度計（Varian Company製造的Cary-5 spectrophotometer），並使用乙酸乙酯溶劑，以0.01g/L的濃度進行測定為較佳。 使用於本發明之光聚合起始劑，亦可根據需要而組合使用2種以上。The ruthenium compound is preferably one having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably having an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably having a higher absorbance at 365 nm and 405 nm. Among the ruthenium compounds, from the viewpoint of sensitivity, the molar absorption coefficient at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and particularly preferably from 5,000 to 200,000. The molar absorption coefficient of the compound can be preferably determined by a known method, for example, using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Company) and using an ethyl acetate solvent at a concentration of 0.01 g/L. The photopolymerization initiator to be used in the present invention may be used in combination of two or more kinds as needed.

光聚合起始劑的含量相對於著色組成物的總固體成分為0.1～50質量%為較佳，0.5～30質量%為更佳，1～20質量%為進一步較佳。在該範圍下，可以獲得更良好之感度和圖案形成性。本發明的著色組成物可以只含有1種光聚合起始劑，亦可含有2種以上。在含有2種以上的情況下，其總量為上述範圍為較佳。The content of the photopolymerization initiator is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, even more preferably from 1 to 20% by mass, based on the total solid content of the coloring composition. Within this range, better sensitivity and pattern formation can be obtained. The colored composition of the present invention may contain only one kind of photopolymerization initiator, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

在本發明中，光聚合起始劑倂用甲醇中的365nm的吸光係數為1.0×103 mL/gcm以上之光聚合起始劑（以下，亦稱作光聚合起始劑（a））和甲醇中的365nm的吸光係數為1.0×102 mL/gcm以下且254nm的吸光係數為1.0×103 mL/gcm以上之光聚合起始劑（以下，亦稱作光聚合起始劑（b））亦較佳。依該態樣，容易形成耐溶劑性優異之硬化膜。 光聚合起始劑（a）的含量在本發明的著色組成物的總固體成分中為1.5～10質量%為較佳，3～8質量%為更佳。只要光聚合起始劑（a）的含量為10質量%以下，感度便良好。又，只要光聚合起始劑（a）的含量為1.5質量%以上，便容易形成耐溶劑性優異之硬化膜。In the present invention, the photopolymerization initiator is a photopolymerization initiator (hereinafter, also referred to as photopolymerization initiator (a)) having an absorption coefficient of 365 nm in methanol of 1.0 × 10 3 mL/gcm or more. a photopolymerization initiator having a light absorption coefficient of 365 nm in methanol of 1.0×10 2 mL/gcm or less and an absorption coefficient of 254 nm of 1.0×10 3 mL/gcm or more (hereinafter, also referred to as photopolymerization initiator (b) ) is also preferred. In this way, it is easy to form a cured film excellent in solvent resistance. The content of the photopolymerization initiator (a) is preferably from 1.5 to 10% by mass, more preferably from 3 to 8% by mass, based on the total solid content of the colored composition of the present invention. When the content of the photopolymerization initiator (a) is 10% by mass or less, the sensitivity is good. In addition, as long as the content of the photopolymerization initiator (a) is 1.5% by mass or more, it is easy to form a cured film excellent in solvent resistance.

光聚合起始劑（a）的甲醇中的365nm的吸光係數為1.0×103 ～1.0×104 mL/gcm為較佳，2.0×103 ～9.0×103 mL/gcm為更佳，6.0×103 ～8.0×103 mL/gcm為進一步較佳。 作為光聚合起始劑（a），能夠適宜地使用肟化合物、胺基苯乙酮化合物以及醯基膦化合物，肟化合物為較佳。作為肟化合物，由上述通式（OX-1）表示之化合物為較佳。 光聚合起始劑（a）的含量在本發明的著色組成物的總固體成分中為1.5～10質量%為較佳，3～8質量%為更佳。只要光聚合起始劑（a）的含量為上述範圍，便容易形成耐溶劑性優異之硬化膜。光聚合起始劑（a）可以單獨使用1種，亦可倂用2種以上。The light absorption coefficient of 365 nm in methanol of the photopolymerization initiator (a) is preferably 1.0 × 10 3 to 1.0 × 10 4 mL / gcm, more preferably 2.0 × 10 3 to 9.0 × 10 3 mL / gcm, 6.0. × 10 3 ~ 8.0 × 10 3 mL / gcm further preferred. As the photopolymerization initiator (a), an anthracene compound, an aminoacetophenone compound, and a mercaptophosphine compound can be suitably used, and an anthracene compound is preferable. As the anthracene compound, a compound represented by the above formula (OX-1) is preferred. The content of the photopolymerization initiator (a) is preferably from 1.5 to 10% by mass, more preferably from 3 to 8% by mass, based on the total solid content of the colored composition of the present invention. When the content of the photopolymerization initiator (a) is in the above range, it is easy to form a cured film excellent in solvent resistance. The photopolymerization initiator (a) may be used singly or in combination of two or more.

光聚合起始劑（b）的甲醇中的365nm的吸光係數為10～1.0×102 mL/gcm為較佳，20～9.0×102 mL/gcm為更佳。 光聚合起始劑（a）的波長365nm的吸光係數與光聚合起始劑（b）的波長365nm的吸光係數之差為9.0×102 mL/gcm以上為較佳，9.0×102 ～1.0×105 mL/gcm為更佳，9.0×102 ～1.0×104 mL/gcm為進一步較佳。 光聚合起始劑（b）的甲醇中的254nm的吸光係數為1.0×103 ～1.0×106 mL/ gcm為較佳，5.0×103 ～1.0×105 mL/ gcm為更佳。 作為光聚合起始劑（b），能夠適宜地使用羥基苯乙酮化合物、胺基苯乙酮化合物以及醯基膦化合物。 羥基苯乙酮化合物為由下述式（V）表示之化合物為較佳。 【化學式50】 The light absorption coefficient at 365 nm in methanol of the photopolymerization initiator (b) is preferably from 10 to 1.0 × 10 2 mL/gcm, more preferably from 20 to 9.0 × 10 2 mL/gcm. The difference between the absorption coefficient at a wavelength of 365 nm of the photopolymerization initiator (a) and the absorption coefficient at a wavelength of 365 nm of the photopolymerization initiator (b) is preferably 9.0 × 10 2 mL/gcm or more, and 9.0 × 10 2 to 1.0. More preferably, 10 5 mL/gcm is more preferably 9.0 × 10 2 to 1.0 × 10 4 mL/gcm. The light absorption coefficient at 254 nm in methanol of the photopolymerization initiator (b) is preferably 1.0 × 10 3 to 1.0 × 10 6 mL / gcm, more preferably 5.0 × 10 3 to 1.0 × 10 5 mL / gcm. As the photopolymerization initiator (b), a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can be suitably used. The hydroxyacetophenone compound is preferably a compound represented by the following formula (V). [Chemical Formula 50]

式（V）中，Rv1 表示氫原子、烷基（碳原子數1～10的烷基為較佳）、烷氧基（碳原子數1～10的烷氧基為較佳）或2價有機基。在Rv1 為2價有機基的情況下，表示2個光活性的羥基苯乙酮結構（亦即，由通式（V）表示之化合物去除取代基Rv1 之結構）經由Rv1 連結而成之二聚物。Rv2 、Rv3 相互獨立地表示氫原子或烷基（碳原子數1～10的烷基為較佳）。又，Rv2 和Rv3 亦可鍵結而形成環（碳原子數4～8的環為較佳）。作為上述Rv1 的烷基以及烷氧基、作為Rv2 以及Rv3 的烷基以及Rv2 與Rv3 鍵結而形成之環亦可進一步具有取代基。In the formula (V), Rv 1 represents a hydrogen atom, an alkyl group (an alkyl group having 1 to 10 carbon atoms is preferred), an alkoxy group (an alkoxy group having 1 to 10 carbon atoms is preferred) or 2 valence. Organic base. When Rv 1 is a divalent organic group, the two photoactive hydroxyacetophenone structures (that is, the structure in which the compound represented by the formula (V) removes the substituent Rv 1 ) are linked via Rv 1 Dimer. Rv 2 and Rv 3 each independently represent a hydrogen atom or an alkyl group (an alkyl group having 1 to 10 carbon atoms is preferred). Further, Rv 2 and Rv 3 may be bonded to each other to form a ring (a ring having 4 to 8 carbon atoms is preferred). The alkyl group and the alkoxy group of Rv 1 , the alkyl group as Rv 2 and Rv 3 , and the ring formed by bonding Rv 2 and Rv 3 may further have a substituent.

光聚合起始劑（b）的含量在本發明的著色組成物的總固體成分中為1.5～7.5質量%為較佳，2～6質量%為更佳。只要光聚合起始劑（b）的含量為上述範圍，便容易形成耐溶劑性優異之硬化膜。光聚合起始劑（b）可以單獨使用1種，亦可倂用2種以上。The content of the photopolymerization initiator (b) is preferably from 1.5 to 7.5% by mass, more preferably from 2 to 6% by mass, based on the total solid content of the colored composition of the present invention. When the content of the photopolymerization initiator (b) is in the above range, it is easy to form a cured film excellent in solvent resistance. The photopolymerization initiator (b) may be used singly or in combination of two or more.

＜＜樹脂＞＞ 本發明的著色組成物含有樹脂為較佳。樹脂例如以使顏料等著色劑分散於組成物中之用途和黏合劑的用途配合。另外，將主要用於分散顏料等著色劑之樹脂亦稱作分散劑。但是，樹脂的該種用途只是一例，還能夠以除了該種用途以外的目的使用。 樹脂的重量平均分子量（Mw）為5000～100,000為較佳。又，數量平均分子量（Mn）為1000～20,000為較佳。<<Resin>> The colored composition of the present invention preferably contains a resin. The resin is blended, for example, in such a manner that a coloring agent such as a pigment is dispersed in a composition and a use of a binder. Further, a resin mainly used for dispersing a coloring agent such as a pigment is also referred to as a dispersing agent. However, such use of the resin is only an example, and it can also be used for purposes other than such use. The weight average molecular weight (Mw) of the resin is preferably from 5,000 to 100,000. Further, the number average molecular weight (Mn) is preferably from 1,000 to 20,000.

本發明的著色組成物中，樹脂相對於著色組成物的總固體成分的含量為5～90質量%為較佳，10～80質量%為更佳。In the colored composition of the present invention, the content of the resin relative to the total solid content of the colored composition is preferably from 5 to 90% by mass, more preferably from 10 to 80% by mass.

＜＜＜分散劑＞＞＞ 本發明的著色組成物在含有顏料的情況下，含有分散劑為較佳。 作為分散劑，可以舉出高分子分散劑〔例如，聚醯胺-胺及其鹽、聚羧酸及其鹽、高分子量不飽和酸酯、改質聚氨酯、改質聚酯、改質聚（甲基）丙烯酸酯、（甲基）丙烯酸系共聚物、萘磺酸福馬林縮合物〕、聚氧乙烯烷基磷酸酯、聚氧乙烯烷基胺、烷醇胺等。 高分子分散劑能夠根據其結構進一步分類為直鏈狀高分子、末端改質型高分子、接枝型高分子、嵌段型高分子。<<<Dispersant>>> When the coloring composition of the present invention contains a pigment, it is preferred to contain a dispersing agent. The dispersing agent may, for example, be a polymer dispersing agent (for example, polyamine-amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, and a modified poly( Methyl) acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine, and the like. The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer according to the structure.

作為末端改質型高分子，例如可以舉出日本特開平3-112992號公報、日本專利公表2003-533455號公報等中記載之在末端具有磷酸基之高分子、日本特開2002-273191號公報等中記載之在末端具有磺酸基之高分子、日本特開平9-77994號公報等中記載之具有有機色素的部分骨架或雜環之高分子等。又，日本特開2007-277514號公報中記載之在高分子末端導入2個以上的對顏料表面的錨錠部位（酸基、鹼性基、有機色素的部分骨架或雜環等）之高分子的分散穩定性亦優異，故較佳。For example, JP-A-2002-273191 discloses a polymer having a phosphate group at a terminal, which is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2003-533455. A polymer having a sulfonic acid group at the terminal, a partial skeleton having an organic dye, or a heterocyclic polymer described in JP-A-9-77994, and the like. Further, a polymer in which two or more anchor sites (acid groups, basic groups, partial skeletons of organic dyes, heterocyclic rings, etc.) on the surface of the pigment are introduced into the polymer terminal, as described in JP-A-2007-277514 The dispersion stability is also excellent, so it is preferred.

作為接枝型高分子，例如可以舉出聚酯系分散劑等。具體而言，可以舉出日本特開昭54-37082號公報、日本專利公表平8-507960號公報、日本特開2009-258668號公報等中記載之聚（低級伸烷基亞胺）與聚酯的反應產物、日本特開平9-169821號公報等中記載之聚烯丙基胺與聚酯的反應產物、日本特開平10-339949號公報、日本特開2004-37986號公報等中記載之巨單體與氮原子單體的共聚物、日本特開2003-238837號公報、日本特開2008-9426號公報、日本特開2008-81732號公報等中記載之具有有機色素的部分骨架或雜環之接枝型高分子、日本特開2010-106268號公報等中記載之巨單體與含酸基單體的共聚物、日本特開2009-203462號公報中記載之具有鹼性基和酸基之兩性分散樹脂等。The graft type polymer may, for example, be a polyester-based dispersant or the like. Specifically, poly(lower alkylene imine) and poly group described in JP-A-H05-370820, JP-A-H08-507960, JP-A-2009-258668, and the like. The reaction product of the ester, and the reaction product of the polyallylamine and the polyester described in JP-A-H09-169821, JP-A-H09-339949, JP-A-2004-37986, and the like. A partial skeleton or an impurity having an organic dye described in JP-A-2003-238732, JP-A-2008-426732, and the like, and a copolymer of a macromonomer and a nitrogen atom. The graft-type polymer of the ring, the copolymer of the macromonomer and the acid group-containing monomer described in JP-A-2010-106268, and the basic group and the acid described in JP-A-2009-203462 The amphoteric dispersion resin and the like.

作為藉由自由基聚合而製造接枝型高分子時使用之巨單體，能夠使用公知的巨單體，可以舉出TOAGOSEI CO.,LTD.製造的巨單體AA-6（末端基為甲基丙烯醯基之聚甲基丙烯酸甲酯）、AS-6（末端基為甲基丙烯醯基之聚苯乙烯）、AN-6S（末端基為甲基丙烯醯基之苯乙烯與丙烯腈的共聚物）、AB-6（末端基為甲基丙烯醯基之聚丙烯酸丁酯）、DAICEL CHEMICAL INDUSTRIES CO.,LTD.製造的PLACCEL FM5（甲基丙烯酸2-羥基乙酯的ε-己內酯5莫耳當量加成物）、FA10L（丙烯酸2-羥基乙酯的ε-己內酯10莫耳當量加成物）以及日本特開平2-272009號公報中記載之聚酯系巨單體等。As a macromonomer used for the production of a graft polymer by radical polymerization, a known macromonomer can be used, and a macromonomer AA-6 (end group A) manufactured by TOAGOSEI CO., LTD. can be used. Acryl fluorenyl polymethyl methacrylate), AS-6 (polystyrene based on methacryl fluorenyl), AN-6S (styrene and acrylonitrile based on methacryl fluorenyl) Copolymer), AB-6 (polybutyl acrylate of methacryl fluorenyl group), PLACEL FM5 manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD. (ε-caprolactone of 2-hydroxyethyl methacrylate) (5 molar equivalent adduct), FA10L (ε-caprolactone 10 molar equivalent of 2-hydroxyethyl acrylate), and polyester macromonomers described in JP-A-2-272009 .

作為嵌段型高分子，日本特開2003-49110號公報、日本特開2009-52010號公報等中記載之嵌段型高分子為較佳。As the block type polymer, a block type polymer described in, for example, JP-A-2003-49110 and JP-A-2009-52010 is preferable.

顏料分散劑亦可作為市售品獲取，作為該種具體例，可以舉出KUSUMOTO Chemicals,LTD.製造的“DA-7301”；BYK-Chemie 公司製造的“Disperbyk-101（聚醯胺-胺磷酸鹽）、107（羧酸酯）、110（含有酸基之共聚物）、130（聚醯胺）、161、162、163、164、165、166、170（高分子共聚物）”、“BYK-P104、P105（高分子量不飽和多羧酸）”、EFKA公司製造的“EFKA4047、4050～4010～4165（聚氨酯系）、EFKA4330～4340（嵌段共聚物）、4400～4402（改質聚丙烯酸酯）、5010（聚酯醯胺）、5765（高分子量聚羧酸鹽）、6220（脂肪酸聚酯）、6745（酞菁衍生物）、6750（偶氮顏料衍生物）”；AJINOMOTO FINE-TECHNO Co.,Inc製造的“AJISPER PB821、PB822、PB880、PB881”；KYOEISHA CHEMICAL CO.,LTD.製造的“FLOWLEN TG-710（氨酯寡聚物）”、“POLYFLOW No.50E、No.300（丙烯酸系共聚物）”；KUSUMOTO Chemicals,Ltd.製造的“DISPARLON KS-860、873SN、874、＃2150（脂肪族多價羧酸）、＃7004（聚醚酯）、DA-703-50、DA-705、DA-725”；KAO Corporation製造的“DEMOL RN、N（萘磺酸福馬林縮聚物）、MS、C、SN-B（芳香族磺酸福馬林縮聚物）”、“HOMOGENOL L-18（高分子聚羧酸）”、“EMULGEN920、930、935、985（聚氧乙烯壬基苯基醚）”、“ACETAMIN86（硬脂基胺乙酸鹽）”；LUBRIZOL JAPAN ,LTD.製造的“SOLSPERSE5000（酞菁衍生物）、22000（偶氮顏料衍生物）、13240（聚酯胺）、3000、17000、27000（在末端部具有功能部之高分子）、24000、28000、32000、38500（接枝型高分子）”；Nikko Chemicals Co., Ltd.製造的“NIKKOR T106（聚氧乙烯山梨糖醇單油酸酯）、MYS-IEX（聚氧乙烯單硬脂酸酯）”；KAWAKEN FINE CHEMICALS CO.,LTD.製造的HINOACT T-8000E等；Shin-Etsu Chemical Co.,Ltd.製造的有機矽氧烷聚合物KP341；YUSHO CO.,LTD.製造的“W001：陽離子系界面活性劑”、聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油烯基醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、脫水山梨糖醇脂肪酸酯等非離子系界面活性劑、“W004、W005、W017”等陰離子系界面活性劑，MORISHITA&CO.,LTD.製造的“EFKA-46、EFKA-47、EFKA-47EA、EFKA聚合物100、EFKA聚合物400、EFKA聚合物401、EFKA聚合物450”、SUN NOPCO LIMITED製造的“DISPERSE AID 6、DISPERSE AID 8、DISPERSE AID 15、DISPERSE AID 9100”等高分子分散劑，ADEKA CORPORATION製造的“ADEKA PLURONIC L31、F38、L42、L44、L61、L64、F68、L72、P95、F77、P84、F87、P94、L101、P103、F108、L121、P-123”、以及SANYO CHEMICAL INDUSTRIES,LTD.製造的“IONET（商品名稱）S-20”等。The pigment dispersant can also be obtained as a commercial product, and as such a specific example, "DA-7301" manufactured by KUSUMOTO Chemicals, LTD.; "Disperbyk-101 (polyamide-amine phosphoric acid) manufactured by BYK-Chemie Co., Ltd. Salt), 107 (carboxylate), 110 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer)", "BYK -P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "EFKA4047, 4050-4010-4165 (polyurethane type), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylic acid) by EFKA company Ester), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative); AJINOMOTO FINE-TECHNO "AJISPER PB821, PB822, PB880, PB881" manufactured by Co., Inc.; "FLOWLEN TG-710 (urethane oligo)", "POLYFLOW No. 50E, No. 300" manufactured by KYOEISHA CHEMICAL CO., LTD. Acrylic copolymer)"; "DISPARLON KS-860, 873SN" manufactured by KUSUMOTO Chemicals, Ltd. 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725"; "DEMOL RN, N (Naphthalenesulfonic acid Fuma) manufactured by KAO Corporation Forest polycondensate), MS, C, SN-B (aromatic sulfonate fumarate polycondensate), "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene) "nonylphenyl ether)", "ACETAMIN86 (stearylamine acetate)"; "SOLSPERSE5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine) manufactured by LUBRIZOL JAPAN, LTD. ), 3000, 17000, 27000 (polymer having a functional portion at the end portion), 24000, 28000, 32000, 38500 (graft-type polymer)"; "NIKKOR T106 (polyoxygen) manufactured by Nikko Chemicals Co., Ltd. Ethylene sorbitol monooleate), MYS-IEX (polyoxyethylene monostearate); HINOACT T-8000E manufactured by KAWAKEN FINE CHEMICALS CO., LTD.; Shin-Etsu Chemical Co., Ltd. Manufactured organic siloxane polymer KP341; "W001: cationic surfactant" manufactured by YUSHO CO., LTD., polyoxyethylene Cinnamyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene Nonionic surfactant such as alcohol distearate or sorbitan fatty acid ester, anionic surfactant such as "W004, W005, W017", "EFKA-46, EFKA- manufactured by MORISHITA & CO., LTD." 47. EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", "DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100" manufactured by SUN NOPCO LIMITED Polymer dispersant, "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" manufactured by ADEKA CORPORATION And "IONET (trade name) S-20" manufactured by SANYO CHEMICAL INDUSTRIES, LTD.

在著色組成物含有分散劑的情況下，分散劑相對於顏料100質量份之含量為1～80質量份為較佳，5～70質量份為更佳，10～60質量份為進一步較佳。When the coloring composition contains a dispersing agent, the content of the dispersing agent is preferably from 1 to 80 parts by mass, more preferably from 5 to 70 parts by mass, even more preferably from 10 to 60 parts by mass, per 100 parts by mass of the pigment.

＜＜＜鹼可溶性樹脂＞＞＞ 本發明的著色組成物能夠含有鹼可溶性樹脂作為樹脂。藉由含有鹼可溶性樹脂，顯影性以及圖案形成性提高。另外，鹼可溶性樹脂亦可用作分散劑和黏合劑。<<<Alkali Soluble Resin>>> The colored composition of the present invention can contain an alkali-soluble resin as a resin. The developability and pattern formability are improved by containing an alkali-soluble resin. In addition, alkali-soluble resins can also be used as a dispersant and a binder.

作為鹼可溶性樹脂的分子量並無特別的限定，重量平均分子量（Mw）為5000～100,000為較佳。又，數量平均分子量（Mn）為1000～20,000為較佳。 作為鹼可溶性樹脂，可以係線性有機高分子聚合物，亦可以從在分子（以丙烯酸系共聚物、苯乙烯系共聚物為主鏈之分子為較佳）中具有至少1個促進鹼可溶性之基團之鹼可溶性樹脂中適當地進行選擇。The molecular weight of the alkali-soluble resin is not particularly limited, and the weight average molecular weight (Mw) is preferably from 5,000 to 100,000. Further, the number average molecular weight (Mn) is preferably from 1,000 to 20,000. The alkali-soluble resin may be a linear organic high molecular polymer, or may have at least one base which promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). The alkaloid-soluble resin is appropriately selected.

作為鹼可溶性樹脂，從耐熱性的觀點來看，聚羥基苯乙烯系樹脂、聚矽氧烷系樹脂、丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯酸/丙烯醯胺共聚物樹脂為較佳，從控制顯影性之觀點來看，丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯酸/丙烯醯胺共聚物樹脂為較佳。 作為促進鹼可溶性之基團（以下，亦稱作酸基），例如可以舉出羧基、磷酸基、磺酸基、酚性羥基等，可溶於有機溶劑中，且可藉由弱鹼水溶液進行顯影者為較佳，作為特佳者可以舉出（甲基）丙烯酸。該些酸基可以僅為1種，亦可以為2種以上。The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of controlling developability, an acrylic resin, an acrylamide resin, and an acrylic/acrylamide copolymer resin are preferable. Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and are soluble in an organic solvent, and can be carried out by a weak alkali aqueous solution. A developer is preferred, and a particularly preferred one is (meth)acrylic acid. These acid groups may be used alone or in combination of two or more.

在製造鹼可溶性樹脂時，例如能夠適用基於公知的自由基聚合法之方法。用自由基聚合法製造鹼可溶性樹脂時的溫度、壓力、自由基起始劑的種類及其量、溶劑的種類等聚合條件可由本領域技術人員容易地設定，亦可以實驗性地設定條件。In the case of producing an alkali-soluble resin, for example, a method based on a known radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art, and the conditions can be experimentally set.

作為鹼可溶性樹脂，在側鏈具有羧酸之聚合物為較佳，可以舉出甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、巴豆酸共聚物、馬來酸共聚物、部分酯化馬來酸共聚物、酚醛清漆型樹脂等鹼可溶性酚樹脂等；以及在側鏈具有羧基之酸性纖維素衍生物、在具有羥基之聚合物上加成酸酐而成者。尤其是（甲基）丙烯酸和可與其共聚合之其他單體的共聚物適合作為鹼可溶性樹脂。作為可與（甲基）丙烯酸共聚合的其他單體，可以舉出（甲基）丙烯酸烷基酯、（甲基）丙烯酸芳基酯、乙烯基化合物等。 作為（甲基）丙烯酸烷基酯以及（甲基）丙烯酸芳基酯，可以舉出（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸己酯、（甲基）丙烯酸辛酯、（甲基）丙烯酸苯酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸甲苯酯、（甲基）丙烯酸萘酯、（甲基）丙烯酸環己酯、甲基丙烯酸縮水甘油酯、甲基丙烯酸四氫糠酯等。作為乙烯基化合物，可以舉出苯乙烯、α-甲基苯乙烯、乙烯基甲苯、丙烯腈、乙酸乙烯酯、N-乙烯基吡咯啶酮、聚苯乙烯巨單體、聚甲基丙烯酸甲酯巨單體等。又，作為能夠與（甲基）丙烯酸共聚之其他單體的例子，可以舉出在日本特開平10-300922號公報中記載之N位取代馬來醯亞胺單體，例如N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等。另外，可與該些（甲基）丙烯酸共聚合之其他單體可以僅為1種，亦可以為2種以上。As the alkali-soluble resin, a polymer having a carboxylic acid in a side chain is preferred, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial ester. An alkali-soluble phenol resin such as a maleic acid copolymer or a novolac type resin; and an acid cellulose derivative having a carboxyl group in a side chain and an acid anhydride added to a polymer having a hydroxyl group. In particular, a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith is suitable as the alkali-soluble resin. Examples of the other monomer copolymerizable with (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid Benzyl ester, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, and the like. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, and polymethyl methacrylate. Giant monomer and so on. In addition, examples of the other monomer which can be copolymerized with (meth)acrylic acid include the N-substituted maleimide monomer described in JP-A-10-300922, for example, N-phenyl horse. Indole imine, N-cyclohexylmaleimide, and the like. Further, the other monomers copolymerizable with the (meth)acrylic acid may be used alone or in combination of two or more.

又，為了提高本發明中之著色組成物的交聯效率，可以使用具有聚合性基團之鹼可溶性樹脂。作為聚合性基團，可以舉出（甲基）烯丙基、（甲基）丙烯醯基等。具有聚合性基團之鹼可溶性樹脂，在側鏈含有聚合性基團之鹼可溶性樹脂等是有用的。 作為含有聚合性基團之鹼可溶性樹脂，可以舉出DIANAL NR系列（MITSUBISHI RAYON CO.,LTD.製造）、Photomer6173（含COOH的polyurethane acrylic oligomer，Diamond Shamrock Co., Ltd.製造）、VISCOAT R-264、KS RESIST 106（均為OSAKA ORGANIC CHEMICAL INDUSTRY LTD.製造）、CYCLOMER P系列（例如ACA230AA）、PLACCEL CF200系列（均為DAICEL CHEMICAL INDUSTRIES CO.,LTD.製造）、Ebecryl 3800（DAICEL UCB CO.,LTD.製造）、Akurikyua-RD-F8(NIPPON SHOKUBAI CO.,LTD.製造)等。Moreover, in order to improve the crosslinking efficiency of the coloring composition in the present invention, an alkali-soluble resin having a polymerizable group can be used. Examples of the polymerizable group include a (meth)allyl group and a (meth)acryl fluorenyl group. An alkali-soluble resin having a polymerizable group is useful as an alkali-soluble resin containing a polymerizable group in a side chain. Examples of the alkali-soluble resin containing a polymerizable group include DIANAL NR series (manufactured by MITSUBISHI RAYON CO., LTD.), Photomer 6173 (polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., Ltd.), and VISCOAT R- 264, KS RESIST 106 (both manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (all manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD.), and Ebecryl 3800 (DAICEL UCB CO., LTD., manufactured by Akurikyua-RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.).

鹼可溶性樹脂可較佳地使用（甲基）丙烯酸苄酯/（甲基）丙烯酸共聚物、（甲基）丙烯酸苄酯/（甲基）丙烯酸/（甲基）丙烯酸-2-羥基乙酯共聚物、由（甲基）丙烯酸苄酯/（甲基）丙烯酸/其他單體構成之多元共聚物。又，亦可以較佳使用將2-羥乙基（甲基）丙烯酸酯共聚合而成者，日本特開平7-140654號公報中記載之（甲基）丙烯酸-2-羥基丙酯/聚苯乙烯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物，丙烯酸-2-羥基-3-苯氧基丙酯/聚甲基丙烯酸甲酯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物，甲基丙烯酸-2-羥基乙酯/聚苯乙烯巨單體/甲基丙烯酸甲酯/甲基丙烯酸共聚物，甲基丙烯酸-2-羥基乙酯/聚苯乙烯巨單體/甲基丙烯酸苄酯/甲基丙烯酸共聚物等。 又，作為市售品，例如還能夠使用ACRYBASE FF-426（FUJIKURAKASEI CO.,LTD.製造）等。As the alkali-soluble resin, benzyl (meth)acrylate/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid/(meth)acrylic acid-2-hydroxyethyl copolymer may be preferably used. a multicomponent copolymer composed of benzyl (meth)acrylate/(meth)acrylic acid/other monomer. Further, it is also possible to use 2-hydroxyethyl (meth) acrylate copolymerized, and 2-hydroxypropyl (meth) acrylate/polyphenyl benzoate described in JP-A-7-140654 Ethylene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid Copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/A Benzyl acrylate / methacrylic acid copolymer and the like. In addition, as a commercial item, for example, ACRYBASE FF-426 (manufactured by FUJIKURAKASEI CO., LTD.) or the like can be used.

鹼可溶性樹脂含有聚合物（a）亦較佳，該聚合物（a）藉由將含有由下述通式（ED1）表示之化合物和/或由下述通式（ED2）表示之化合物（以下，有時亦將該些化合物稱作“醚二聚物”）之單體成分聚合而構成。It is also preferred that the alkali-soluble resin contains a polymer (a) which contains a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (below) Further, the monomer components of these compounds are sometimes referred to as "ether dimers".

【化學式51】 [Chemical Formula 51]

通式（ED1）中，R1 以及R2 分別獨立地表示氫原子或可以具有取代基之碳原子數為1～25的烴基。 【化學式52】通式（ED2）中，R表示氫原子或碳原子數為1～30的有機基。作為通式（ED2）的具體例，可以參閱日本特開2010-168539號公報的記載。In the formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. [Chemical Formula 52] In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Specific examples of the general formula (ED2) can be referred to the description of JP-A-2010-168539.

通式（ED1）中，作為由R1 以及R2 表示之可以具有取代基之碳原子數為1～25的烴基並無特別的限制，例如可以舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、叔丁基、叔戊基、硬脂基、月桂基、2-乙基己基等直鏈狀或支鏈狀的烷基；苯基等芳基；環己基、叔丁基環己基、二環戊二烯基、三環癸烷基、異冰片基、金剛烷基、2-甲基-2-金剛烷基等脂環式基團；經1-甲氧基乙基、1-乙氧基乙基等烷氧基取代之烷基；經苄基等芳基取代之烷基等。其中，從耐熱性的觀點來看，如甲基、乙基、環己基、苄基等不易因酸或熱而脫離之一級或二級碳的取代基為特佳。In the general formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 1 and R 2 is not particularly limited, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. a linear or branched alkyl group such as isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl or 2-ethylhexyl; an aryl group such as phenyl; An alicyclic group such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl or 2-methyl-2-adamantyl; An alkyl group substituted with an alkoxy group such as a methoxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group or the like. Among them, from the viewpoint of heat resistance, a substituent such as a methyl group, an ethyl group, a cyclohexyl group, a benzyl group or the like which is not easily separated from a primary or secondary carbon by acid or heat is particularly preferable.

作為醚二聚物的具體例，例如可參閱日本特開2013-29760號公報的段落號0317，該內容編入本說明書中。醚二聚物可以僅為1種，亦可以為2種以上。源自由通式（ED）表示之化合物的結構體亦可以使其他單體共聚合。Specific examples of the ether dimer can be referred to, for example, in paragraph 0317 of JP-A-2013-29760, which is incorporated herein by reference. The ether dimer may be used alone or in combination of two or more. The structure of the compound represented by the free radical formula (ED) may also copolymerize other monomers.

鹼可溶性樹脂亦可以含有源自由下述式（X）表示之化合物之結構單元。 【化學式53】在式（X）中，R1 表示氫原子或甲基，R2 表示碳原子數為2～10的伸烷基，R3 表示氫原子或可以含有苯環的碳原子數為1～20的烷基。n表示1～15的整數。The alkali-soluble resin may also contain a structural unit derived from a compound represented by the following formula (X). [Chemical Formula 53] In the formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 represents a hydrogen atom or may have a benzene ring having 1 to 20 carbon atoms. alkyl. n represents an integer of 1 to 15.

在上述式（X）中，R2 的伸烷基的碳原子數為2～3為較佳。又，R3 的烷基的碳原子數為1～20，1～10為更佳，R3 的烷基亦可以含有苯環。作為由R3 表示之含有苯環之烷基，可以舉出苄基、2-苯基（異）丙基等。In the above formula (X), the alkylene group of R 2 has preferably 2 to 3 carbon atoms. Further, the alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and the alkyl group of R 3 may contain a benzene ring. The alkyl group containing a benzene ring represented by R 3 may, for example, be a benzyl group or a 2-phenyl(iso)propyl group.

鹼可溶性樹脂可以參閱日本特開2012-208494號公報段落號0558～0571（對應之美國專利申請公開第2012/0235099號說明書的[0685]～[0700]）之後的記載，將該些內容編入本申請案說明書中。 另外，亦可使用日本特開2012-32767號公報中記載之段落號0029～0063中記載之共聚物（B）以及實施例中使用之鹼可溶性樹脂、日本特開2012-208474號公報的段落號0088～0098中記載之黏合劑樹脂以及實施例中使用之黏合劑樹脂、日本特開2012-137531號公報的段落號0022～0032中記載之黏合劑樹脂以及在實施例中使用之黏合劑樹脂、日本特開2013-024934號公報的段落號0132～0143中記載之黏合劑樹脂以及在實施例中使用之黏合劑樹脂、日本特開2011-242752號公報的段落號0092～0098中記載之黏合劑樹脂以及實施例中使用之黏合劑樹脂、日本特開2012-032770號公報的段落號0030～0072中記載之黏合劑樹脂。將該些內容編入本申請案說明書中。The alkali-soluble resin can be referred to in the following paragraphs of JP-A-2012-208494, paragraphs 0558 to 0571 (corresponding to [0685] to [0700] of the specification of the US Patent Application Publication No. 2012/0235099), and the contents are incorporated herein. In the application note. In addition, the copolymer (B) described in paragraphs 0029 to 0063 described in JP-A-2012-32767, and the alkali-soluble resin used in the examples, and the paragraph number of JP-A-2012-208474 can be used. The adhesive resin described in 0088 to 0098 and the adhesive resin used in the examples, the adhesive resin described in paragraphs 0022 to 0032 of JP-A-2012-137531, and the adhesive resin used in the examples, The adhesive resin described in paragraphs 0132 to 0143 of JP-A-2013-024934, and the adhesive resin used in the examples, and the adhesives described in paragraphs 0092 to 0098 of JP-A-2011-242752 The resin and the binder resin used in the examples, and the binder resin described in paragraphs 0030 to 0072 of JP-A-2012-032770. This content is incorporated into the specification of the present application.

鹼可溶性樹脂的酸值為30～500mgKOH/g為較佳。下限為50mgKOH/g以上為更佳，70mgKOH/g以上為進一步較佳。上限為400mgKOH/g以下為更佳，200mgKOH/g以下為進一步較佳，150mgKOH/g以下為特佳，120mgKOH/g以下為更進一步較佳。The acid value of the alkali-soluble resin is preferably from 30 to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. The upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and even more preferably 120 mgKOH/g or less.

在著色組成物含有鹼可溶性樹脂之情況下，鹼可溶性樹脂的含量相對於著色組成物的總固體成分為1～15質量%為較佳，2～12質量%為更佳，3～10質量%為進一步較佳。本發明的著色組成物可以僅含有1種鹼可溶性樹脂，亦可以含有2種以上。在含有2種以上鹼可溶性樹脂之情況下，其總量成為上述範圍為較佳。When the coloring composition contains an alkali-soluble resin, the content of the alkali-soluble resin is preferably 1 to 15% by mass based on the total solid content of the coloring composition, more preferably 2 to 12% by mass, and 3 to 10% by mass. It is further preferred. The colored composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. In the case where two or more kinds of alkali-soluble resins are contained, the total amount thereof is preferably in the above range.

＜＜顏料衍生物＞＞ 本發明的著色組成物含有顏料衍生物為較佳。顏料衍生物為具有由酸性基、鹼性基或鄰苯二甲醯亞胺甲基取代有機顏料的一部分之結構之化合物為較佳。作為顏料衍生物，從著色劑A的分散性以及分散穩定性的觀點來看，具有酸性基或鹼性基之顏料衍生物為較佳。具有鹼性基之顏料衍生物為特佳。又，就上述樹脂（分散劑）與顏料衍生物的組合而言，分散劑為酸性分散劑且顏料衍生物具有鹼性基之組合為較佳。<<Pigment Derivative>> The coloring composition of the present invention preferably contains a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of the organic pigment is substituted by an acidic group, a basic group or a phthalimine methyl group. As the pigment derivative, a pigment derivative having an acidic group or a basic group is preferred from the viewpoint of dispersibility of the colorant A and dispersion stability. Pigment derivatives having a basic group are particularly preferred. Further, in the combination of the above resin (dispersant) and the pigment derivative, it is preferred that the dispersant is an acidic dispersant and the pigment derivative has a combination of basic groups.

作為用於構成顏料衍生物的有機顏料，可以舉出二酮吡咯并吡咯系顏料、偶氮系顏料、酞菁系顏料、蒽醌系顏料、喹吖啶酮系顏料、二噁嗪系顏料、紫環酮系顏料、苝系顏料、硫靛系顏料、異吲哚啉系顏料、異吲哚啉酮系顏料、喹酞酮系顏料、士林系顏料、金屬絡合物系顏料等。 又，作為顏料衍生物所具有之酸性基，磺酸基、羧酸基及其鹽為較佳，羧酸基以及磺酸基為進一步較佳，磺酸基為特佳。作為顏料衍生物所具有之鹼性基，氨基為較佳，三級氨基為特佳。Examples of the organic pigment constituting the pigment derivative include a diketopyrrolopyrrole pigment, an azo pigment, a phthalocyanine pigment, an anthraquinone pigment, a quinacridone pigment, and a dioxazine pigment. A purple ring ketone pigment, an anthraquinone pigment, a thioindole pigment, an isoporphyrin pigment, an isoindolinone pigment, a quinophthalone pigment, a Shilin pigment, a metal complex pigment, and the like. Further, as the acidic group of the pigment derivative, a sulfonic acid group, a carboxylic acid group and a salt thereof are preferred, and a carboxylic acid group and a sulfonic acid group are further preferred, and a sulfonic acid group is particularly preferred. As the basic group of the pigment derivative, an amino group is preferred, and a tertiary amino group is particularly preferred.

在本發明的著色組成物含有顏料衍生物之情況下，顏料衍生物的含量相對於顏料的質量為1～30質量%為較佳，3～20質量%為進一步較佳。顏料衍生物可以僅使用1種，亦可以併用2種以上。In the case where the colored composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably from 1 to 30% by mass, more preferably from 3 to 20% by mass, based on the mass of the pigment. The pigment derivative may be used alone or in combination of two or more.

＜＜有機溶劑＞＞ 本發明的著色組成物亦可含有有機溶劑。 有機溶劑只要滿足各成分的溶解性或著色組成物的塗佈性，便基本上無特別限制，但考慮著色劑、硬化性化合物等的溶解性、塗佈性、安全性而選擇為較佳。<<Organic solvent>> The coloring composition of the present invention may also contain an organic solvent. The organic solvent is not particularly limited as long as it satisfies the solubility of each component or the coating property of the coloring composition, but is preferably selected in consideration of solubility, coatability, and safety of a coloring agent and a curable compound.

作為有機溶劑可以適宜地舉出如下：酯類例如：乙酸乙酯、乙酸正丁酯、乙酸異丁酯、乙酸環己酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、氧基乙酸烷基酯類（例：氧基乙酸甲酯、氧基乙酸乙酯、氧基乙酸丁酯（例如，甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等））、3-氧基丙酸烷基酯類（例：3-氧基丙酸甲酯、3-氧基丙酸乙酯等（例如，3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯等））、2-氧基丙酸烷基酯類（例：2-氧基丙酸甲酯、2-氧基丙酸乙酯、2-氧基丙酸丙酯等（例如，2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯））、2-氧基-2-甲基丙酸甲酯以及2-氧基-2-甲基丙酸乙酯（例如，2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等）、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-丁酮酸甲酯、2-丁酮酸乙酯等；以及醚類例如：二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單***、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、丙二醇單甲醚、丙二醇甲醚乙酸酯、丙二醇***乙酸酯、丙二醇丙醚乙酸酯等；以及酮類例如：甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮等；以及芳香族烴類例如：甲苯、二甲苯等。The organic solvent can be suitably exemplified as follows: esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, butyric acid Propyl ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg , methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate ( Examples: methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl ester, ethyl 3-ethoxypropionate, etc.), alkyl 2-oxopropionate (eg methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxygen) Propyl propyl propionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -ethyl ethoxypropionate)), methyl 2-oxy-2-methylpropanoate and 2-oxy-2-methyl Ethyl propionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, acetone Acid propyl ester, ethyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-butyrate acid, ethyl 2-butyrate acid, etc.; and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene Alcohol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl Ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, etc.; and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-glycol Ketone, 3-heptanone, etc.; and aromatic hydrocarbons such as toluene, xylene, and the like.

從色素（A）、硬化性化合物等的溶解性、塗佈面狀的改善等的觀點來看，該些有機溶劑混合2種以上亦較佳。在該情況下，由選自上述3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基溶纖劑乙酸酯、乳酸乙酯、二乙二醇二甲醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇甲醚、以及丙二醇甲醚乙酸酯之2種以上構成之混合溶液為特佳。 在本發明中，過氧化物在有機溶劑中的含有率為0.8mmol/L以下為較佳，實質上不含有過氧化物為更佳。From the viewpoints of the solubility of the dye (A), the curable compound, and the like, and the improvement of the coating surface, it is preferred to mix two or more kinds of these organic solvents. In this case, it is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, Butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether A mixed solution of two or more kinds of acid esters is particularly preferable. In the present invention, the content of the peroxide in the organic solvent is preferably 0.8 mmol/L or less, and it is more preferable that the peroxide is substantially not contained.

從塗佈性的觀點來看，有機溶劑在著色組成物中的含量設成著色組成物的總固體成分濃度成為5～80質量%之量為較佳，5～60質量%為進一步較佳，10～50質量%為特佳。 本發明的著色組成物可以只含有1種有機溶劑，亦可含有2種以上。在含有2種以上的情況下，其總量為上述範圍為較佳。The content of the organic solvent in the coloring composition is preferably from 5 to 80% by mass based on the total solid content of the coloring composition, and more preferably from 5 to 60% by mass. 10 to 50% by mass is particularly preferred. The colored composition of the present invention may contain only one type of organic solvent, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

＜＜聚合抑制劑＞＞ 在本發明的著色組成物中，為了在著色組成物的製造中或保存中阻止聚合性化合物的不必要的熱聚合，理想的是添加少量的聚合抑制劑。 作為聚合抑制劑，可以舉出對苯二酚、對甲氧基苯酚、二-叔丁基對甲酚、鄰苯三酚、叔丁基鄰苯二酚、苯醌、4,4’-硫代雙（3-甲基-6-叔丁基苯酚）、2,2’-伸甲基雙（4-甲基-6-叔丁基苯酚）、N-亞硝基苯基羥胺第一鈰鹽等。 在本發明的著色組成物含有聚合抑制劑之情況下，聚合抑制劑的含量相對於著色組成物的質量為0.01～5質量%為較佳。 本發明的著色組成物可以僅含有1種聚合抑制劑，亦可以含有2種以上。在含有2種以上聚合抑制劑之情況下，其總量成為上述範圍為較佳。<<Polymerization inhibitor>> In the colored composition of the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable compound during production or storage of the colored composition, it is preferred to add a small amount of a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-sulfur. Di-bis(3-methyl-6-tert-butylphenol), 2,2'-methyl bis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first Salt and so on. In the case where the coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably from 0.01 to 5% by mass based on the mass of the coloring composition. The colored composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types of polymerization inhibitors are contained, the total amount thereof is preferably in the above range.

＜＜界面活性劑＞＞ 從進一步提高塗佈性之觀點來看，亦可以向本發明的著色組成物中添加各種界面活性劑。作為界面活性劑，可以使用氟系界面活性劑、非離子系界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑、矽酮系界面活性劑等各種界面活性劑。<<Interfacial Active Agent>> From the viewpoint of further improving the coatability, various surfactants may be added to the colored composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

例如，藉由含有氟系界面活性劑，製備成塗佈液時的液體特性（尤其是流動性）進一步提高。亦即，在使用含有氟系界面活性劑之著色組成物而形成膜之情況下，藉由使被塗佈面與塗佈液之間的界面張力減小，對被塗佈面的潤濕性得到改善，對被塗佈面的塗佈性提高。因此，即使在以少量的液體量形成數μm左右的薄膜時，亦能更適宜地形成厚度不均較少且均勻厚度的膜這一點上是有效的。For example, by containing a fluorine-based surfactant, liquid characteristics (especially fluidity) at the time of preparation of a coating liquid are further improved. In other words, when a film is formed using a coloring composition containing a fluorine-based surfactant, the wettability of the surface to be coated is reduced by reducing the interfacial tension between the surface to be coated and the coating liquid. It is improved and the coating property to the coated surface is improved. Therefore, even when a film having a thickness of about several μm is formed with a small amount of liquid, it is effective to form a film having a small thickness unevenness and a uniform thickness.

氟系界面活性劑中的氟含有率為3～40質量%為適宜，5～30質量%為更佳，7～25質量%為特佳。氟含有率為該範圍內之氟系界面活性劑在塗佈膜的厚度均勻性、省液性方面是有效的，且著色組成物中之溶解性亦良好。The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass, more preferably from 5 to 30% by mass, and particularly preferably from 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content in this range is effective in thickness uniformity and liquid-saving property of the coating film, and the solubility in the colored composition is also good.

作為氟系界面活性劑，例如可以舉出：MEGAFAC F171、MEGAFAC F172、MEGAFAC F173、MEGAFAC F176、MEGAFAC F177、MEGAFAC F141、MEGAFAC F142、MEGAFAC F143、MEGAFAC F144、MEGAFAC R30、MEGAFAC F437、MEGAFAC F475、MEGAFAC F479、MEGAFAC F482、MEGAFAC F554、MEGAFAC F780、MEGAFAC F781（以上，DIC Corporation製造）；FLUORAD FC430、FLUORAD FC431、FLUORAD FC171（以上，SUMITOMO 3M Limited製造）；SURFLON S-382、SURFLON SC-101、SURFLON SC-103、SURFLON SC-104、SURFLON SC-105、SURFLON SC1068、SURFLON SC-381、SURFLON SC-383、SURFLON S393、SURFLON KH-40（以上，ASAHI GLASS CO.,LTD.製造）；PolyFox（註冊商標） PF-636、PF-656、PF-6320、PF-6520、PF-7002（OMNOVA Solutions Inc.製造）等。 氟系界面活性劑還能夠使用日本特開2010-32698號公報中記載之氟系界面活性劑。 氟系界面活性劑還能夠使用嵌段聚合物，作為具體例，例如可以舉出日本特開2011-89090號公報中記載之化合物。 氟系界面活性劑還能夠較佳地使用含有具有氟原子之（甲基）丙烯酸酯化合物衍生之重複單元和具有2個以上（5個以上為較佳）伸烷氧基（乙烯氧基和/或丙烯氧基為較佳）之（甲基）丙烯酸酯化合物衍生之重複單元之含氟高分子化合物。 又，還能夠將在側鏈具有乙烯性不飽和基之含氟聚合物用作氟系界面活性劑。作為具體例，可以舉出日本特開2010-164965號公報0050～0090段落以及0289～0295段落中記載之化合物，例如DIC Corporation製造的MEGAFAC RS-101、RS-102、RS-718K等。Examples of the fluorine-based surfactant include MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141, MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437, MEGAFAC F475, and MEGAFAC F479. , MEGAFAC F482, MEGAFAC F554, MEGAFAC F780, MEGAFAC F781 (above, manufactured by DIC Corporation); FLUORAD FC430, FLUORAD FC431, FLUORAD FC171 (above, manufactured by SUMITOMO 3M Limited); SURFLON S-382, SURFLON SC-101, SURFLON SC- 103, SURFLON SC-104, SURFLON SC-105, SURFLON SC1068, SURFLON SC-381, SURFLON SC-383, SURFLON S393, SURFLON KH-40 (above, manufactured by ASAHI GLASS CO., LTD.); PolyFox (registered trademark) PF-636, PF-656, PF-6320, PF-6520, PF-7002 (manufactured by OMNOVA Solutions Inc.), and the like. The fluorine-based surfactant described in JP-A-2010-32698 can also be used as the fluorine-based surfactant. As the fluorine-based surfactant, a block polymer can also be used. Specific examples thereof include a compound described in JP-A-2011-89090. The fluorine-based surfactant can also preferably use a repeating unit derived from a (meth) acrylate compound having a fluorine atom and have two or more (more preferably 5 or more) alkoxy groups (vinyloxy group and/or Or a fluoropolymer compound in which a repeating unit derived from a (meth) acrylate compound is preferably a propyleneoxy group. Further, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as the fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965, for example, MEGAFAC RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

作為非離子系界面活性劑，具體可以舉出甘油、三羥甲基丙烷、三羥甲基乙烷以及該等之乙氧基化物以及丙氧基化物（例如丙氧基化甘油、乙氧基化甘油等）、聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油烯基醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、脫水山梨糖醇脂肪酸酯（BASF 公司製造的PLURONIC L10、L31、L61、L62、10R5、17R2、25R2、TETRONIC 304、701、704、901、904、150R1）、SOLSPERSE 20000（LUBRIZOL JAPAN ,LTD.）等。又，亦可使用TAKEMOTO OIL＆FAT CO.,LTD.製造的PIONIN D-6112-W、Wako Pure Chemical Industries, Ltd.製造的NCW-101、NCW-1001、NCW-1002。Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and the like, and ethoxylates (for example, propoxylated glycerin, ethoxylate). Glycerol, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, 901 manufactured by BASF Corporation) , 904, 150R1), SOLSPERSE 20000 (LUBRIZOL JAPAN, LTD.), and the like. Further, PIONIN D-6112-W manufactured by TAKEMOTO OIL & FAT CO., LTD., NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

作為陽離子系界面活性劑，具體而言，可以舉出酞菁衍生物（商品名稱：EFKA-745、MORISHITA & CO.,LTD.製造）、有機矽氧烷聚合物KP341（Shin-Etsu Chemical Co., Ltd.製造）、（甲基）丙烯酸系（共）聚合物POLYFLOW No.75、No.90、No.95（KYOEISHA CHEMICAL CO.,LTD.製造）、W001（YUSHO CO.,LTD.製造）等。Specific examples of the cation-based surfactant include a phthalocyanine derivative (trade name: EFKA-745, manufactured by MORISHITA & CO., LTD.), and an organic siloxane polymer KP341 (Shin-Etsu Chemical Co.). , manufactured by Ltd., (meth)acrylic (co)polymer POLYFLOW No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD.), W001 (manufactured by YUSHO CO., LTD.) Wait.

作為陰離子系界面活性劑，具體可以舉出W004、W005、W017（YUSHO CO.,LTD.製造）等。Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by YUSHO CO., LTD.).

作為矽酮系界面活性劑，例如可以舉出：DOW CORNING TORAY CO.,LTD.製造的“TORAY SILICONE DC3PA”、“TORAY SILICONE SH7PA”、“TORAY SILICONE DC11PA”、“TORAY SILICONE SH21PA”、“TORAY SILICONE SH28PA”、“TORAY SILICONE SH29PA”、“TORAY SILICONE SH30PA”、“TORAY SILICONE SH8400”；MOMENTIVE PERFORMANCE MATERIALS Inc.製造的“TSF-4440”、“TSF-4300”、“TSF-4445”、“TSF-4460”、“TSF-4452”； Shin-Etsu Chemical Co., Ltd.製造的“KP341”、“KF6001”、“KF6002”；BYK Chemie CO.,LTD.製造的“BYK307”、“BYK323”、“BYK330”等。Examples of the anthrone-based surfactants include "TORAY SILICONE DC3PA", "TORAY SILICONE SH7PA", "TORAY SILICONE DC11PA", "TORAY SILICONE SH21PA", and "TORAY SILICONE" manufactured by DOW CORNING TORAY CO., LTD. SH28PA", "TORAY SILICONE SH29PA", "TORAY SILICONE SH30PA", "TORAY SILICONE SH8400"; "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460" manufactured by MOMENTIVE PERFORMANCE MATERIALS Inc. ""TSF-4452"; "KP341", "KF6001", "KF6002" manufactured by Shin-Etsu Chemical Co., Ltd.; "BYK307", "BYK323", "BYK330" manufactured by BYK Chemie CO., LTD. "Wait.

在本發明的著色組成物含有界面活性劑之情況下，界面活性劑相對於著色組成物的總質量之含量為0.001～2.0質量%為較佳，0.005～1.0質量%為更佳。 本發明的著色組成物可以僅含有1種界面活性劑，亦可以含有2種以上。在含有2種以上界面活性劑之情況下，其總量成為上述範圍為較佳。When the coloring composition of the present invention contains a surfactant, the content of the surfactant to the total mass of the coloring composition is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass. The colored composition of the present invention may contain only one type of surfactant, or may contain two or more types. In the case where two or more kinds of surfactants are contained, the total amount thereof is preferably in the above range.

＜＜其他添加劑＞＞ 在本發明的著色組成物中，可以根據需要而能夠配合各種添加物，例如填充劑、黏附促進劑、抗氧化劑、紫外線吸收劑、凝集抑制劑等。作為該些添加物，可以舉出日本特開2004-295116號公報的段落號0155～0156中記載者，將該些內容編入本申請說明書中。 在本發明的著色組成物中，能夠含有在日本特開2004-295116號公報的段落號0078中記載之增感劑和光穩定劑、在前述公報的段落號0081中記載之熱聚合抑制劑。<<Other Additives>> In the colored composition of the present invention, various additives such as a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended as needed. The above-mentioned additives are described in paragraphs 0155 to 0156 of JP-A-2004-295116, and the contents are incorporated in the specification of the present application. The coloring composition of the present invention can contain the sensitizer and the light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of the above publication.

根據所使用之原料等，有時在著色組成物中含有金屬元素，但從抑制發生缺陷等的觀點來看，著色組成物中的第2族元素（鈣、鎂等）的含量為50ppm以下為較佳，控制到0.01～10ppm更為佳。又，著色組成物中的無機金屬鹽的総量為100ppm以下為較佳，控制到0.5～50ppm為更佳。The content of the second group element (calcium, magnesium, etc.) in the coloring composition is 50 ppm or less, from the viewpoint of suppressing occurrence of defects or the like, depending on the raw material to be used. Preferably, it is more preferably controlled to 0.01 to 10 ppm. Further, the amount of the inorganic metal salt in the colored composition is preferably 100 ppm or less, and more preferably 0.5 to 50 ppm.

＜著色組成物的製備方法＞ 本發明的著色組成物藉由混合前述成分而製備。 在製備著色組成物時，可以統括配合構成著色組成物之各成分，亦可以在將各成分溶解、分散於溶劑中之後逐次進行配合。又，配合時的放入順序、作業條件不受特別制約。例如可以將所有成分同時溶解、分散於溶劑中而製備組成物，根據需要，亦可以將各成分適當地設成2種以上的溶液、分散液，並在使用時（塗佈時）將該些進行混合而製備組成物。 以去除異物和減少缺陷等目的，本發明的著色組成物用過濾器進行過濾為較佳。作為過濾器，只要是一直以來在過濾用途等中所使用者，則可以無特別限定地使用。例如可以舉出由聚四氟乙烯（PTFE）等氟樹脂、尼龍（例如尼龍-6、尼龍-6,6）等聚醯胺系樹脂、聚乙烯、聚丙烯（PP）等聚烯烴樹脂（包含高密度、超高分子量）等構成之過濾器。該些原材料中聚丙烯（包含高密度聚丙烯）以及尼龍為較佳。 過濾器的孔徑為0.01～7.0μm左右比較合適，0.01～3.0μm左右為較佳，0.05～0.5μm左右為進一步較佳。藉由設成該範圍，能夠可靠地去除在後製程中阻礙製備均勻以及平滑的著色組成物之微細的異物。又，使用纖維狀的過濾材料亦較佳，作為過濾材料，例如可以舉出聚丙烯纖維、尼龍纖維、玻璃纖維等，具體而言，能夠使用ROKI TECHNO CO.,LTD. 製造的SBP類型系列（SBP008等）、TPR類型系列（TPR002、TPR005等）、SHPX類型系列（SHPX003等）濾芯。<Method for Preparing Colored Composition> The colored composition of the present invention is prepared by mixing the above components. In the preparation of the colored composition, each component constituting the colored composition may be blended in the entirety, or may be blended after the components are dissolved and dispersed in a solvent. Moreover, the order of placement and the working conditions at the time of fitting are not particularly restricted. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a composition, and if necessary, each component may be appropriately prepared into two or more kinds of solutions and dispersions, and these may be used at the time of application (at the time of coating). The composition was prepared by mixing. The coloring composition of the present invention is preferably filtered with a filter for the purpose of removing foreign matter and reducing defects. The filter can be used without any particular limitation as long as it is used by a user for filtration or the like. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6 or nylon-6,6), or a polyolefin resin such as polyethylene or polypropylene (PP) may be mentioned. A filter composed of high density, ultra high molecular weight, and the like. Among these raw materials, polypropylene (including high density polypropylene) and nylon are preferred. The pore diameter of the filter is preferably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm. By setting this range, it is possible to reliably remove fine foreign matter which hinders preparation of a uniform and smooth coloring composition in the post-process. In addition, a fibrous filter material is also preferably used, and examples of the filter material include polypropylene fiber, nylon fiber, and glass fiber. Specifically, an SBP type series manufactured by ROKI TECHNO CO., LTD. SBP008, etc., TPR type series (TPR002, TPR005, etc.), SHPX type series (SHPX003, etc.) filter element.

在使用過濾器時，亦可以組合不同的過濾器來使用。此時，藉由第1過濾器的過濾可以僅進行1次，亦可以進行2次以上。 又，亦可以在上述範圍內組合不同孔徑的第1過濾器。此處的孔徑可參閱過濾器製造商的標稱值。作為市售的過濾器，例如能夠從NIHON PALL LTD.、ADVANTECH TOYO KAISHA,LTD.、NIHON ENTEGRIS K.K.（以前的Mykrolis Corporation）或KITZ MICROFILTER CORPORATION 等提供之各種過濾器中選擇。 第2過濾器可使用由與上述第1過濾器相同材料等形成者。 例如可以只利用分散液進行藉由第1過濾器的過濾，在混合其他成分之後，進行第2的過濾。When using a filter, it is also possible to combine different filters for use. At this time, the filtration by the first filter may be performed only once, or may be performed twice or more. Further, the first filter having a different pore diameter may be combined within the above range. The aperture here can be found in the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD., ADVANTECH TOYO KAISHA, LTD., NIHON ENTEGRIS K.K. (formerly Mykrolis Corporation) or KITZ MICROFILTER CORPORATION. The second filter can be formed of the same material or the like as the first filter described above. For example, the filtration by the first filter may be performed only by the dispersion, and after the other components are mixed, the second filtration may be performed.

＜彩色濾光片、圖案形成方法、彩色濾光片的製造方法＞ 接著，對本發明的彩色濾光片、圖案形成方法以及彩色濾光片的製造方法進行詳細敘述。又，對使用本發明的圖案形成方法之彩色濾光片的製造方法亦進行說明。<Color Filter, Pattern Forming Method, and Method of Manufacturing Color Filter> Next, the color filter, the pattern forming method, and the method of producing the color filter of the present invention will be described in detail. Further, a method of manufacturing a color filter using the pattern forming method of the present invention will also be described.

本發明的彩色濾光片係使用本發明的著色組成物而成者。 本發明的圖案形成方法能夠經由如下製程而製造：使用本發明的著色組成物，在支撐體上形成著色組成物層之製程；將著色組成物層曝光成圖案狀之製程；以及對未曝光部進行顯影去除而形成著色圖案之製程。而且，亦可根據需要，設置對著色組成物層進行烘烤之製程（預烘烤製程）以及對顯影之著色圖案進行烘烤之製程（後烘烤製程）。以下，對各製程進行詳細敘述。The color filter of the present invention is obtained by using the colored composition of the present invention. The pattern forming method of the present invention can be produced by a process of forming a colored composition layer on a support using the colored composition of the present invention; a process of exposing the colored composition layer into a pattern; and an unexposed portion A process of developing and removing to form a colored pattern is performed. Further, a process of baking the coloring composition layer (prebaking process) and a process of baking the developed coloring pattern (post-baking process) may be provided as needed. Hereinafter, each process will be described in detail.

＜＜形成著色組成物層之製程＞＞ 在形成著色組成物層之製程中，使用本發明的著色組成物，在支撐體上形成著色組成物層。<<Process for Forming Colored Composition Layer>> In the process of forming the colored composition layer, the colored composition layer of the present invention is used to form a colored composition layer on the support.

作為支撐體，例如能夠舉出玻璃、矽、聚碳酸酯、聚酯、芳香族聚醯胺、聚醯胺醯亞胺、聚醯亞胺等透明基板。亦可在該些透明基板上形成用於驅動有機EL元件之薄膜電晶體。 又，能夠使用在基板上設置有CCD或CMOS等固體攝像元件（受光元件）之固體攝像元件用基板。Examples of the support include transparent substrates such as glass, ruthenium, polycarbonate, polyester, aromatic polyamine, polyamidimide, and polyimine. A thin film transistor for driving the organic EL element may also be formed on the transparent substrates. Further, a substrate for a solid-state imaging device in which a solid-state imaging device (light-receiving element) such as a CCD or a CMOS is provided on a substrate can be used.

作為將本發明的著色組成物應用於支撐體上之方法，能夠使用狹縫塗佈、噴墨法、旋轉塗佈、流延塗佈、輥塗佈、絲網印刷法等各種方法。As a method of applying the coloring composition of the present invention to a support, various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be used.

對形成於支撐體上之著色組成物層進行加熱（預烘烤）為較佳。以120℃以下進行加熱為較佳，50～120℃為更佳，80～110℃為進一步較佳，90～105℃為特佳。藉由以120℃以下進行加熱，在將有機EL元件用作圖像顯示装置的發光光源的情況，或者在由有機原材料構成圖像感測器的光電轉換膜的情況下，能夠更加有效地維持該些的特性。 加熱時間為10秒～300秒為較佳，40～250秒為更佳，80～220秒為進一步較佳。能夠利用加熱板、烘箱等進行加熱。It is preferred to heat (pre-bake) the colored composition layer formed on the support. Heating at 120 ° C or lower is preferred, 50 to 120 ° C is more preferred, 80 to 110 ° C is further preferred, and 90 to 105 ° C is particularly preferred. By heating at 120 ° C or lower, in the case where the organic EL element is used as a light-emitting source of an image display device, or in the case of a photoelectric conversion film in which an image sensor is composed of an organic material, it can be more effectively maintained. These characteristics. The heating time is preferably from 10 seconds to 300 seconds, more preferably from 40 to 250 seconds, and further preferably from 80 to 220 seconds. Heating can be performed by a hot plate, an oven, or the like.

＜＜曝光製程＞＞ 接著，將形成於支撐體上之著色組成物層呈圖案狀進行曝光（曝光製程）。例如對形成於支撐體上之著色組成物層，使用步進機等曝光裝置，經由具有規定的遮罩圖案之遮罩進行曝光，藉此能夠進行圖案曝光。藉此能夠使曝光部分硬化。 作為可以在曝光時使用之放射線（光），使用g線、i線等紫外線為較佳（i線為特佳）。照射量（曝光量）例如為0.03～2.5J/cm2 為較佳，0.05～1.0J/cm2 為更佳，0.08～0.5J/cm2 為最佳。 能夠適當地選擇曝光時的氧濃度，除了在大氣下進行之外，例如還可以在氧濃度為19體積%以下的低氧氣氛下(例如，15體積%、5體積%、實質上無氧)進行曝光，亦可在氧濃度超過21體積%之高氧氣氛下（例如，22體積%、30體積%、50體積%)進行曝光。又，能夠適當地設定曝光照度，通常能夠從1000W/m2 ～100000W/m2 (例如，5000W/m2 、15000W/m2 、35000W/m2 )的範圍選擇。氧濃度和曝光照度可以適當地組合條件，例如在氧濃度為10體積%時，照度可設為10000W/m2 ，在氧濃度為35體積%時，照度可設為20000W/m2 等。<<Exposure Process>> Next, the colored composition layer formed on the support is exposed in a pattern (exposure process). For example, the coloring composition layer formed on the support can be exposed by exposure using a mask having a predetermined mask pattern by using an exposure device such as a stepping machine. Thereby, the exposed portion can be hardened. As the radiation (light) which can be used for exposure, it is preferable to use ultraviolet rays such as g-line or i-line (i-line is particularly preferable). Irradiation amount (exposure amount) is, for example 0.03 ~ 2.5J / cm 2 is preferred, 0.05 ~ 1.0J / cm 2 is more preferably, 0.08 ~ 0.5J / cm 2 is optimal. The oxygen concentration at the time of exposure can be appropriately selected, and it can be carried out under a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free), in addition to being carried out in the atmosphere. Exposure may also be carried out under a high oxygen atmosphere (for example, 22% by volume, 30% by volume, 50% by volume) having an oxygen concentration of more than 21% by volume. Further, the exposure illuminance can be appropriately set, and can be generally selected from the range of 1000 W/m 2 to 100000 W/m 2 (for example, 5000 W/m 2 , 15000 W/m 2 , and 35000 W/m 2 ). The oxygen concentration and exposure illuminance may be appropriately combined conditions, for example an oxygen concentration of 10 vol%, the illuminance may be set 10000W / m 2, when an oxygen concentration of 35 vol%, the illuminance may be set 20000W / m 2 and the like.

硬化膜的膜厚為1.0μm以下為較佳，0.1～0.9μm為更佳，0.2～0.8μm為進一步較佳。藉由將膜厚設為1.0μm以下，容易獲得高解析度、高密合性。The film thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 to 0.9 μm, and still more preferably 0.2 to 0.8 μm. By setting the film thickness to 1.0 μm or less, it is easy to obtain high resolution and high adhesion.

＜＜顯影製程＞＞ 接著，對未曝光部進行顯影去除，形成著色圖案。能夠使用顯影液對未曝光部進行顯影去除。藉此，曝光製程中的未曝光部的著色組成物層溶出於顯影液，僅殘留光硬化之部分。 作為顯影液，不會對基底的固體攝像元件或電路等造成損傷之有機鹼性顯影液為較佳。 顯影液的溫度例如為20～30℃為較佳。顯影時間為20～180秒為較佳。<<Developing Process>> Next, the unexposed portion is developed and removed to form a colored pattern. The unexposed portion can be removed by development using a developer. Thereby, the colored composition layer of the unexposed portion in the exposure process is dissolved in the developer, and only the portion where the light is hardened remains. As the developer, an organic alkaline developer which does not damage the solid image sensor or the circuit of the substrate is preferable. The temperature of the developer is preferably, for example, 20 to 30 °C. The development time is preferably from 20 to 180 seconds.

作為使用於顯影液之鹼劑，例如可以舉出氨水、乙胺、二乙胺、二甲基乙醇胺、氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨、氫氧化芐基三甲基銨、膽鹼、吡咯、哌啶、1,8-二氮雜雙環[5,4,0]-7-十一碳烯等有機鹼性化合物。以濃度成為0.001～10質量%（0.01～1質量%為較佳）的方式用純水稀釋該些鹼劑而得到之鹼性水溶液較佳地用作顯影液。 又，亦可在顯影液中使用無機鹼。作為無機鹼，例如氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、矽酸鈉、偏矽酸鈉等為較佳。 又，亦可在顯影液中使用界面活性劑。作為界面活性劑的例子，可以舉出前述之界面活性劑，非離子系界面活性劑為較佳。在顯影液含有界面活性劑的情況下，相對於顯影液的總質量，0.001～2.0質量%為較佳，0.01～1.0質量%為更佳。 另外，在使用由該種鹼性水溶液構成之顯影液的情況下，一般在顯影之後，用純水進行清洗（沖洗）為較佳。Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and hydroxide. An organic basic compound such as tetrabutylammonium, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo[5,4,0]-7-undecene. The alkaline aqueous solution obtained by diluting the alkali agents with pure water so as to have a concentration of 0.001 to 10% by mass (preferably 0.01 to 1% by mass) is preferably used as a developing solution. Further, an inorganic base may be used in the developer. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate or the like is preferable. Further, a surfactant may be used in the developer. Examples of the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferred. When the developer contains a surfactant, it is preferably 0.001 to 2.0% by mass, more preferably 0.01 to 1.0% by mass, based on the total mass of the developer. Further, in the case of using a developing solution composed of such an alkaline aqueous solution, it is generally preferred to carry out washing (rinsing) with pure water after development.

在顯影之後，在實施乾燥之後進行加熱處理（後烘烤）為較佳。若要形成多色著色圖案，則能夠對每個顏色依次重複進行製程而製造硬化膜。藉此，可以獲得彩色濾光片。 後烘烤為用於促進硬化的顯影後的加熱處理，加熱溫度例如為100～240℃為較佳。又，在將有機EL元件用作圖像顯示装置的發光光源的情況或由有機原材料構成圖像感測器的光電轉換膜的情況下，在50～120℃（80～100℃為更佳，80～90℃為進一步較佳）下進行加熱處理（後烘烤）為較佳。 能夠使用加熱板或對流式烘箱（熱風循環式乾燥機）、高頻加熱機等加熱機構，以成為上述條件之方式，以連續式或分批式對顯影後的膜進行後烘烤處理。After the development, it is preferred to carry out heat treatment (post-baking) after performing the drying. To form a multi-color shading pattern, it is possible to repeat the process for each color to produce a cured film. Thereby, a color filter can be obtained. The post-baking is a heat treatment after development for promoting hardening, and the heating temperature is preferably, for example, 100 to 240 °C. Further, in the case where the organic EL element is used as the light-emitting source of the image display device or the photoelectric conversion film of the image sensor is composed of the organic material, it is preferably 50 to 120 ° C (80 to 100 ° C, It is preferred to carry out heat treatment (post-baking) at 80 to 90 ° C for further improvement. The film after development can be post-baked in a continuous or batch manner using a heating means such as a hot plate or a convection oven (hot air circulation dryer) or a high-frequency heater.

又，在本發明中，在將聚合性化合物用作硬化性化合物且使用含有上述光聚合起始劑（a）和光聚合起始劑（b）之著色組成物的情況下，在上述曝光製程中，亦可利用大於350nm且380nm以下波長的光（波長為355～370nm的光為較佳，i線為特佳）進行曝光，利用波長為254～350nm的光（波長為254nm的光為較佳），對顯影製程後的著色組成物層進一步進行曝光亦較佳。 又，在上述顯影製程前的曝光中使用之光的波長與在顯影製程後的曝光中使用之光的波長之差為200nm以下為較佳，100～150nm以下為更佳。 藉由以顯影製程前以及顯影製程後這2個段階對著色組成物層進行曝光，能夠藉由最初的曝光使著色組成物適當地硬化，能夠藉由下一次曝光使著色組成物整體大致硬化。其結果，即使在沒有210℃左右的後烘烤的低溫條件下，亦能夠提高著色組成物的硬化性，能夠使彩色濾光片的耐溶劑性變得良好。又，還能夠抑制與其他顏色之間的混色。Further, in the present invention, in the case where a polymerizable compound is used as the curable compound and a coloring composition containing the photopolymerization initiator (a) and the photopolymerization initiator (b) is used, in the above exposure process It is also possible to use light having a wavelength of more than 350 nm and 380 nm (light having a wavelength of 355 to 370 nm is preferable, and i-line is particularly preferable), and light having a wavelength of 254 to 350 nm (light having a wavelength of 254 nm is preferable). Further, it is also preferable to further expose the colored composition layer after the development process. Further, the difference between the wavelength of the light used for the exposure before the development process and the wavelength of the light used for the exposure after the development process is preferably 200 nm or less, more preferably 100 to 150 nm or less. By exposing the colored composition layer to the two steps before the development process and after the development process, the colored composition can be appropriately cured by the first exposure, and the entire coloring composition can be substantially cured by the next exposure. As a result, even in a low-temperature condition without post-baking at about 210 ° C, the curability of the colored composition can be improved, and the solvent resistance of the color filter can be improved. Moreover, it is also possible to suppress color mixture with other colors.

在進行顯影製程前的曝光時，大於350nm且380nm以下波長的光的照射量（曝光量）為30mJ/cm2 ～1500mJ/cm2 為較佳，50mJ/cm2 ～1000mJ/cm2 為更佳。 又，在顯影製程前的曝光時聚合性化合物的反應率為30～60%為較佳。藉由設成該種反應率，能夠使聚合性化合物成為適當地硬化之狀態。在此，具有聚合性化合物之化合物的反應率係指，聚合性化合物所具有之總不飽和雙鍵中已反應之不飽和雙鍵的比例。In the exposure before the development process, the irradiation amount (exposure amount) of light having a wavelength of more than 350 nm and 380 nm or less is preferably 30 mJ/cm 2 to 1500 mJ/cm 2 , more preferably 50 mJ/cm 2 to 1000 mJ/cm 2 . . Further, the reaction rate of the polymerizable compound at the time of exposure before the development process is preferably from 30 to 60%. By setting such a reaction rate, the polymerizable compound can be appropriately cured. Here, the reaction rate of the compound having a polymerizable compound means the ratio of the reacted unsaturated double bond in the total unsaturated double bond of the polymerizable compound.

在進行顯影製程後的曝光時，波長為254～300nm的光的照射量（曝光量）為30mJ/cm2 ～4000mJ/cm2 為較佳，50mJ/cm2 ～3500mJ/cm2 為更佳。 又，在顯影製程後的曝光時聚合性化合物的反應率為60～90%為較佳。藉由設成該種反應率，能夠使曝光後的著色組成物層的硬化狀態變得更加良好。In the exposure after the development process, the irradiation amount (exposure amount) of light having a wavelength of 254 to 300 nm is preferably 30 mJ/cm 2 to 4000 mJ/cm 2 , more preferably 50 mJ/cm 2 to 3500 mJ/cm 2 . Further, the reaction rate of the polymerizable compound at the time of exposure after the development process is preferably from 60 to 90%. By setting such a reaction rate, the cured state of the colored composition layer after exposure can be further improved.

在該態樣中，亦可在進行顯影製程後的曝光之後，進一步進行後烘烤，但在將有機EL元件用作圖像顯示装置的發光光源的情況或由有機原材料構成圖像感測器的光電轉換膜的情況下，在50～120℃（80～100℃為更佳，80～90℃為進一步較佳）下進行加熱處理（後烘烤）為較佳。In this aspect, post-baking may be further performed after the exposure after the development process, but the image sensor is composed of an organic EL element as an illuminating light source of the image display device or an organic material. In the case of the photoelectric conversion film, heat treatment (post-baking) is preferably carried out at 50 to 120 ° C (more preferably 80 to 100 ° C, and more preferably 80 to 90 ° C).

本發明的彩色濾光片可適宜地應用於CCD、CMOS等固體攝像元件中，尤其適用於超過100萬畫素之高解析度的CCD、CMOS等中。本發明的彩色濾光片例如可用作在構成CCD或CMOS之各畫素的受光部與用於聚光的微透鏡之間配置之彩色濾光片。The color filter of the present invention can be suitably applied to a solid-state imaging device such as a CCD or a CMOS, and is particularly suitable for use in a high-resolution CCD, CMOS or the like of more than one million pixels. The color filter of the present invention can be used, for example, as a color filter disposed between a light receiving portion constituting each pixel of a CCD or CMOS and a microlens for collecting light.

又，本發明的彩色濾光片能夠較佳地用於有機EL元件。作為有機EL元件，白色有機EL元件為較佳。有機EL元件為串聯結構為較佳。關於有機EL元件的串聯結構，在日本特開2003-45676號公報、三上明義監修、“有機EL技術開發的前沿-高亮度・高精度・長寿命化・經驗集-”、技術資訊協會、326-328頁、2008年等中有所記載。作為有機EL元件的串聯結構，例如可以舉出在基板的一面中在具有光反射性之下部電極與具有光透射性之上部電極之間設置有機EL層之結構等。下部電極由在可見光的波長區域中具有充分之反射率之材料構成為較佳。有機EL層含有複數個發光層，且具有該些複數個發光層層疊而成之層疊結構（串聯結構）為較佳。有機EL層例如能夠在複數個發光層中包括紅色發光層、綠色發光層以及藍色發光層。而且，除了具有複數個發光層之外，該些同時具有用於使發光層發光之複數個發光輔助層為較佳。有機EL層例如能夠設為發光層與發光輔助層交替層疊之層疊結構。具有該種結構的有機EL層之有機EL元件能夠發出白色光。在該情況下，有機EL元件所發出之白色光的光譜係，在藍色區域（430nm-485nm）、綠色區域（530nm-580nm）以及黄色區域（580nm-620nm）具有較強之最大發光峰值者為較佳。係除了具有該些發光峰值之外，進一步在紅色區域（650nm-700nm）具有最大發光峰值者為更佳。藉由組合發出白色光之有機EL元件（白色有機EL元件）和本發明的彩色濾光片，可以獲得色彩再現性優異之分光特性，能夠顯示更加鮮明的影像或圖像。Further, the color filter of the present invention can be preferably used for an organic EL element. As the organic EL element, a white organic EL element is preferable. It is preferred that the organic EL element has a series structure. The series structure of the organic EL device is disclosed in Japanese Patent Laid-Open Publication No. 2003-45676, Sansei Mingji, "The Frontier of Organic EL Technology Development - High Brightness, High Accuracy, Long Life, and Experience Collection", and the Technical Information Association. It is recorded in pages 326-328 and 2008. The tandem structure of the organic EL element includes, for example, a structure in which an organic EL layer is provided between a light-reflecting lower electrode and a light-transmitting upper electrode on one surface of the substrate. The lower electrode is preferably made of a material having a sufficient reflectance in a wavelength region of visible light. The organic EL layer contains a plurality of light-emitting layers, and a laminated structure (series structure) in which the plurality of light-emitting layers are laminated is preferable. The organic EL layer can include, for example, a red light-emitting layer, a green light-emitting layer, and a blue light-emitting layer among a plurality of light-emitting layers. Further, in addition to having a plurality of light-emitting layers, it is preferable to have a plurality of light-emitting auxiliary layers for causing the light-emitting layer to emit light. The organic EL layer can be, for example, a laminated structure in which a light-emitting layer and a light-emitting auxiliary layer are alternately laminated. The organic EL element having the organic EL layer of such a structure can emit white light. In this case, the spectrum of the white light emitted by the organic EL element has a strong maximum luminescence peak in the blue region (430 nm - 485 nm), the green region (530 nm - 580 nm), and the yellow region (580 nm - 620 nm). It is better. In addition to having such luminescence peaks, it is more preferable to further have a maximum luminescence peak in the red region (650 nm to 700 nm). By combining the organic EL element (white organic EL element) that emits white light and the color filter of the present invention, it is possible to obtain a spectral characteristic excellent in color reproducibility, and to display a more vivid image or image.

本發明的彩色濾光片中之著色圖案（著色畫素）的膜厚為2.0μm以下為較佳，1.0μm以下為更佳，0.7μm以下為進一步較佳。下限例如能夠設為0.1μm以上，亦可以設為0.2μm以上。 又，作為著色圖案（著色畫素）的尺寸（圖案寬度），2.5μm以下為較佳，2.0μm以下為更佳，1.7μm以下為特佳。下限例如可以設為0.1μm以上，亦可以設為0.2μm以上。The coloring pattern (colored pixel) of the color filter of the present invention has a film thickness of preferably 2.0 μm or less, more preferably 1.0 μm or less, and further preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more. Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less. The lower limit can be, for example, 0.1 μm or more, or 0.2 μm or more.

＜固體攝像元件＞ 本發明的固體攝像元件具備上述本發明的彩色濾光片。作為本發明的固體攝像元件的構成，只要是具備本發明的彩色濾光片且作為固體攝像元件而發揮功能之構成，則無特別的限定，例如可以舉出如以下構成。<Solid-State Imaging Device> The solid-state imaging device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has a color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration is possible.

如下構成：在支撐體上具有構成固體攝像元件（CCD圖像感測器、CMOS圖像感測器等）的受光區域之複數個光電二極體、以及由多晶矽等構成之轉移電極，在光電二極體以及轉移電極上具有僅使光電二極體的受光部開口之由鎢等構成之遮光膜，在遮光膜上具有以覆蓋遮光膜整個面以及光電二極體受光部的方式形成之由氮化矽等構成之裝置保護膜，在裝置保護膜上具有本發明的固體攝像元件用彩色濾光片。 另外，亦可以為在裝置保護層上且彩色濾光片的下側（接近支撐體的一側）具有聚光機構（例如微透鏡等。以下相同）之構成、或在彩色濾光片上具有聚光機構之構成等。A plurality of photodiodes constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode made of a polycrystalline silicon or the like are provided on the support, and the photoelectric The polarizer and the transfer electrode have a light-shielding film made of tungsten or the like which opens only the light-receiving portion of the photodiode, and the light-shielding film is formed to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. A device protective film made of tantalum nitride or the like has a color filter for a solid-state imaging device of the present invention on a device protective film. Further, it may be configured to have a light collecting means (for example, a microlens or the like, the same below) on the protective layer of the device and on the lower side of the color filter (the side close to the support), or may have a color filter. The composition of the concentrating mechanism, and the like.

＜圖像顯示裝置＞ 本發明的彩色濾光片能夠使用於液晶顯示裝置、有機電致發光顯示裝置等圖像顯示裝置。<Image Display Device> The color filter of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device.

關於顯示裝置的定義、各顯示裝置的詳細內容，例如記載於“電子顯示器裝置（佐々木 昭夫 著，Kogyo Chosakai Publishing Co.,Ltd.，1990年發行）”、“顯示器裝置（伊吹 順章著、Sangyo Tosho Co.,Ltd.，平成元年發行）”等。又，關於液晶顯示裝置，例如記載於“下一代液晶顯示器技術（內田 龍男編輯、Kogyo Chosakai Publishing Co.,Ltd.，1994年發行）”。本發明能夠適用之液晶顯示裝置並無特別的限制，例如能夠適用於上述“下一代液晶顯示器技術”中記載之各種方式的液晶顯示裝置。The definition of the display device and the details of each display device are described, for example, in "Electronic display device (Kogyo Chosakai Publishing Co., Ltd., issued in 1990)", "Display device (Ibuki Shunzhang, Sangyo) Tosho Co., Ltd., issued in the first year of Heisei)" and so on. Further, the liquid crystal display device is described, for example, in "Next-Generation Liquid Crystal Display Technology (Edited by Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next-generation liquid crystal display technology".

本發明的彩色濾光片亦可使用於彩色TFT（Thin Film Transistor）方式的液晶顯示裝置。關於彩色TFT方式的液晶顯示裝置，例如記載於“彩色TFT液晶顯示器（KYORITSU SHUPPAN CO.,LTD.，1996年發行）”。另外，本發明亦可以適用於IPS（In Plane Switching）等橫向電場驅動方式、MVA（Multi-domain Vertical Alignment）等畫素分割方式等的視角被擴大之液晶顯示裝置、或STN（Super-Twist Nematic）、TN（Twisted Nematic）、VA（Vertical Alignment）、OCS（on-chip spacer）、FFS（fringe field switching）、以及R-OCB（Reflective Optically Compensated Bend）等中。 又，本發明之彩色濾光片亦可以提供於明亮且高清晰之COA（Color-filter On Array）方式。在COA方式的液晶顯示裝置中，對彩色濾光片層之要求特性除了如前述之通常的要求特性以外，有時還需要對層間絶縁膜之要求特性，亦即低介電常數以及剝離液耐性。本發明的彩色濾光片由於耐光性等優異，因此能夠提供解析度高、長期耐久性優異之COA方式的液晶顯示裝置。另外，為了滿足低介電常數的要求特性，亦可以在彩色濾光片層之上設置樹脂覆膜。 關於該些圖像顯示方式，例如記載於“EL、PDP、LCD顯示器-技術與市場的最新動向-（Toray Research Center,Inc.調査研究部門，2001年發行）”的43頁等。The color filter of the present invention can also be used in a liquid crystal display device of a color TFT (Thin Film Transistor) type. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (KYORITSU SHUPPAN CO., LTD., issued in 1996)". In addition, the present invention is also applicable to a liquid crystal display device in which a viewing angle such as a horizontal electric field driving method such as IPS (In Plane Switching) or a pixel division method such as MVA (Multi-domain Vertical Alignment) is expanded, or STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optically Compensated Bend). Moreover, the color filter of the present invention can also be provided in a bright and high-resolution COA (Color-filter On Array) method. In the COA liquid crystal display device, in addition to the usual required characteristics as described above, the required characteristics of the color filter layer may be required for the interlayer insulating film, that is, the low dielectric constant and the peeling liquid resistance. . Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA liquid crystal display device having high resolution and excellent long-term durability. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin coating may be provided on the color filter layer. These image display methods are described, for example, on page 43 of "EL, PDP, LCD Display - Technology and Market Trends - (Toray Research Center, Inc. Survey and Research Department, issued in 2001)".

具備本發明之彩色濾光片之液晶顯示裝置，除了本發明之彩色濾光片以外，還藉由電極基板、偏光膜、相位差膜、背光裝置、間隔件（Spacer）、視角保障膜等各種構件所構成。本發明的彩色濾光片能夠適用於由該些公知的構件構成之液晶顯示裝置。關於該些構件，例如記載於“’94液晶顯示器周邊材料以及化學產品的市場（島 健太郎 CMC CO.,LTD.1994年發行）”、“2003液晶關連市場的現狀以及未來展望（下卷）（表良吉 FUJI CHIMERA RESEARCH INSTITUTE, INC.，2003年發行）”。 關於背光，記載於SID meeting Digest 1380（2005）（A.Konno et.al）、月刊顯示器2005年12月號的18～24頁（島 康裕）、月刊顯示器2005年12月號的25～30頁（八木隆明）等。The liquid crystal display device including the color filter of the present invention includes, in addition to the color filter of the present invention, an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle assurance film, and the like. Constructed by components. The color filter of the present invention can be applied to a liquid crystal display device composed of such known members. These components are described, for example, in "94 Markets for Liquid Crystal Display Peripherals and Chemical Products (issued by Kanda Co., Ltd., CMC CO., LTD.)", "2003 Current Status and Future Prospects of Liquid Crystal Related Markets (Vol. 2)" "FUJI CHIMERA RESEARCH INSTITUTE, INC., issued in 2003)". The backlight is described in SID meeting Digest 1380 (2005) (A. Konno et. al), monthly publication December 2005, pages 18 to 24 (Island Kang Yu), monthly publication, December 2005 issue, 25 to 30 pages. (Yamamu Longming) and so on.

若將本發明之彩色濾光片使用於液晶顯示裝置，則與以往公知的冷陰極管的三波長管組合時能夠實現較高的對比度，另外，藉由將紅、緑、藍的二極體光源（RGB-LED）作為背光，能夠提供亮度較高且色彩純度較高的色彩再現性良好的液晶顯示裝置。 【實施例】When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a conventional three-wavelength tube of a cold cathode tube, and red, green, and blue diodes can be used. The light source (RGB-LED) functions as a backlight, and is capable of providing a liquid crystal display device having high brightness and high color reproducibility. [Examples]

以下，例舉實施例對本發明進行更具體的說明。以下實施例中所示之材料、使用量、比例、處理內容、處理順序等，只要不脱離本發明的趣旨，則能夠適當地進行變更。從而，本發明的範圍係並非限定於以下所示之具體例者。另外，只要沒有特別的說明，則“份”、“ %”為質量基準。Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the invention is not limited to the specific examples shown below. In addition, unless otherwise indicated, "part" and "%" are mass standards.

＜重量平均分子量的測定＞ 藉由以下方法測定重量平均分子量。 色譜柱的種類：連結TOSOH TSKgel Super HZM-H、TOSOH TSKgel Super HZ4000以及TOSOH TSKgel Super HZ2000之色譜柱 展開溶劑：四氫呋喃 色譜柱溫度：40℃ 流量（樣品注入量）：1.0μL（樣品濃度：0.1質量%） 装置名稱：TOSOH Corporation製造 HLC-8220GPC 檢測器：RI（折射率）檢測器 校準曲線基礎樹脂：聚苯乙烯<Measurement of Weight Average Molecular Weight> The weight average molecular weight was measured by the following method. Column type: Column TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000 Development solvent: Tetrahydrofuran Column temperature: 40 °C Flow rate (sample injection amount): 1.0 μL (sample concentration: 0.1 mass) %) Device name: HLC-8220GPC manufactured by TOSOH Corporation Detector: RI (refractive index) detector calibration curve Base resin: polystyrene

（C.I.顏料藍15:6（PB15:6）顏料分散液的製備） 將由15份作為顏料的顏料藍15:6、50份作為樹脂（分散劑）的Disperbyk-161（BYKChemie 公司製造）、35份作為溶劑的丙二醇單甲醚乙酸酯（PGMEA）構成之混合液，藉由珠磨機混合並分散15小時，製備出PB15:6顏料分散液。(Preparation of CI Pigment Blue 15:6 (PB15:6) Pigment Dispersion) Disperbyk-161 (manufactured by BYK Chemie Co., Ltd.), 35 parts of 15 parts of pigment blue 15:6, 50 parts as a resin (dispersant) A mixture of propylene glycol monomethyl ether acetate (PGMEA) as a solvent was mixed and dispersed by a bead mill for 15 hours to prepare a PB15:6 pigment dispersion.

（C.I.顏料紫23（PV23）顏料分散液的製備） 將由15份顏料紫23、50份作為樹脂（分散劑）的Disperbyk-161（BYKChemie 公司製造）、35份作為溶劑的丙二醇單甲醚乙酸酯（PGMEA）構成之混合液，藉由珠磨機混合並分散15小時，製備出PV23顏料分散液。(Preparation of CI Pigment Violet 23 (PV23) Pigment Dispersion) Disperbyk-161 (manufactured by BYK Chemie Co., Ltd.) containing 15 parts of Pigment Violet 23, 50 parts as a resin (dispersant), and 35 parts of propylene glycol monomethyl ether acetate as a solvent A mixture of esters (PGMEA) was mixed and dispersed by a bead mill for 15 hours to prepare a PV23 pigment dispersion.

（著色組成物的製備） 混合下述各成分而獲得著色組成物。 【表1】 【表2】 (Preparation of Colored Composition) Each of the following components was mixed to obtain a colored composition. 【Table 1】 【Table 2】

上述表中所示之成分記號分別表示下述化合物。 （色素A） A-1：下述結構（色素多聚物，重量平均分子量=12000，同時記載於主鏈的重複單元之數値為質量比。） 【化學式54】A-2：下述結構（色素多聚物，重量平均分子量=13200，同時記載於主鏈的重複單元之數値為質量比。） 【化學式55】A-3：下述結構（色素多聚物，重量平均分子量=13200，同時記載於主鏈的重複單元之數値為質量比。） 【化學式56】A-4：下述結構（色素單量體） 【化學式57】A-5：下述結構（色素多聚物，重量平均分子量=10800，同時記載於主鏈的重複單元之數値為質量比。） 【化學式58】A-6：下述結構（色素多聚物，重量平均分子量=9300，同時記載於主鏈的重複單元之數値為質量比。） 【化學式59】A-7：下述結構（色素多聚物（具有三芳基甲烷骨架/甲基丙烯酸/聚合性基之單元的質量比=43.15/13.2/25.93），重量平均分子量=8200） 【化學式60】A-8：下述結構（色素多聚物，重量平均分子量=11300） 【化學式61】A-9：下述結構（色素多聚物，重量平均分子量=10100，同時記載於主鏈的重複單元之數値為質量比） 【化學式62】 The component symbols shown in the above table indicate the following compounds, respectively. (Pigment A) A-1: the following structure (pigment polymer, weight average molecular weight = 12,000, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 54] A-2: the following structure (pigment polymer, weight average molecular weight = 13200, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 55] A-3: the following structure (pigment polymer, weight average molecular weight = 13200, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 56] A-4: The following structure (pigment single body) [Chemical Formula 57] A-5: the following structure (pigment polymer, weight average molecular weight = 10,800, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 58] A-6: the following structure (pigment polymer, weight average molecular weight = 9300, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 59] A-7: the following structure (mass polymer (mass ratio of unit having triarylmethane skeleton/methacrylic acid/polymerizable group = 43.15/13.2/25.93), weight average molecular weight=8200) [Chemical Formula 60] A-8: the following structure (pigment polymer, weight average molecular weight = 11300) [Chemical Formula 61] A-9: the following structure (pigment polymer, weight average molecular weight = 10,100, and the number of repeating units described in the main chain is mass ratio) [Chemical Formula 62]

（色素B） B-1：下述結構（色素多聚物，重量平均分子量=12000，同時記載於主鏈的重複單元之數値為質量比。） 【化學式63】B-2：下述結構（色素多聚物，重量平均分子量=13200，同時記載於主鏈的重複單元之數値為質量比。） 【化學式64】B-3：下述結構（色素多聚物，重量平均分子量=13200，同時記載於主鏈的重複單元之數値為質量比。） 【化學式65】B-4：下述結構（色素多聚物（呫噸骨架/甲基丙烯酸/甲基丙烯酸與甲基丙烯酸縮水甘油酯的加合物的莫耳比=5/6/6，甲基丙烯酸衍生的重複單元以及甲基丙烯酸與甲基丙烯酸縮水甘油酯的加合物衍生的重複單元的平均個數為12個），重量平均分子量=11600） 【化學式66】B-5：下述結構（色素單量體） 【化學式67】B-6：下述結構（色素多聚物，重量平均分子量=11000，同時記載於主鏈的重複單元之數値為質量比。） 【化學式68】B-7：下述結構（色素多聚物，重量平均分子量=9100，同時記載於主鏈的重複單元之數値為質量比。） 【化學式69】B-8：下述結構（色素多聚物（具有呫噸骨架/甲基丙烯酸/聚合性基之單元的質量比=46.42/12.44/24.44），重量平均分子量=8900） 【化學式70】B-9：下述結構（色素多聚物，重量平均分子量=13500） 【化學式71】B-10：下述結構（色素多聚物，重量平均分子量=14100） 【化學式72】B-11：下述結構（色素多聚物，重量平均分子量=8500，同時記載於主鏈的重複單元之數値為質量比。） 【化學式73】 (Pigment B) B-1: The following structure (pigment polymer, weight average molecular weight = 12,000, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 63] B-2: the following structure (pigment polymer, weight average molecular weight = 13200, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 64] B-3: the following structure (pigment polymer, weight average molecular weight = 13200, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 65] B-4: The following structure (coloring polymer (xanthene skeleton / methacrylic acid / methacrylic acid and glycidyl methacrylate adduct molar ratio = 5 / 6 / 6, methacrylic acid derived The repeating unit and the average number of repeating units derived from the adduct of methacrylic acid and glycidyl methacrylate are 12), and the weight average molecular weight is 11600) [Chemical Formula 66] B-5: The following structure (coloring unit) [Chemical Formula 67] B-6: the following structure (pigment polymer, weight average molecular weight = 11,000, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 68] B-7: the following structure (pigment polymer, weight average molecular weight = 9100, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 69] B-8: the following structure (mass polymer (mass ratio of unit having xanthene skeleton/methacrylic acid/polymerizable group = 46.42/12.44/24.44), weight average molecular weight=8900) [Chemical Formula 70] B-9: the following structure (pigment polymer, weight average molecular weight = 13500) [Chemical Formula 71] B-10: the following structure (pigment polymer, weight average molecular weight = 14100) [Chemical Formula 72] B-11: the following structure (pigment polymer, weight average molecular weight = 8500, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 73]

（其他色素多聚物） C-1：下述結構（重量平均分子量=13200，同時記載於主鏈的重複單元之數値為質量比。） 【化學式74】 (Other pigment polymer) C-1: The following structure (weight average molecular weight = 13200, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 74]

（樹脂） D-1：ACRYCURE-RD-F8（NIPPON SHOKUBAI CO., LTD.製造，重量平均分子量=11000） D-2：ACRYBASE FF-426（FUJIKURAKASEI CO.,LTD.製造，重量平均分子量=14000） D-3：下述結構（重量平均分子量=11000，同時記載於主鏈的重複單元之數値為質量比。） 【化學式75】D-4：下述結構（重量平均分子量=12000，同時記載於主鏈的重複單元之數値為質量比。） 【化學式76】（硬化性化合物） E-1：KARAYAD　DPHA　（NIPPON KAYAKU CO.,LTD.製造，單體，分子量=562） E-2：ARONIX TO-2349（TOAGOSEI CO.,LTD.製造，單體，分子量=625） E-3：NK酯A-DPH-12E（SHIN-NAKAMURA CHEMICAL CO.,LTD.製造，單體，分子量=1107） E-4：NK酯A-TMMT（SHIN-NAKAMURA CHEMICAL CO.,LTD.製造，單體，分子量=352）（光聚合起始劑） F-1：IRGACURE-OXE01（BASF 公司製造） F-2：IRGACURE-OXE02（BASF 公司製造） F-3：IRGACURE-369（BASF 公司製造） F-4：下述化合物 【化學式77】（界面活性劑） W-1：下述混合物（Mw=14000） 【化學式78】W-2： PolyFox（註冊商標）　PF-6320　（OMNOVA Solutions Inc.製造） （溶劑） PGMEA：丙二醇單甲醚乙酸酯(Resin) D-1: ACRYCURE-RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD., weight average molecular weight = 11000) D-2: ACRYBASE FF-426 (manufactured by FUJIKURAKASEI CO., LTD., weight average molecular weight = 14000) D-3: the following structure (weight average molecular weight = 11,000, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 75] D-4: the following structure (weight average molecular weight = 12,000, and the number of repeating units described in the main chain is a mass ratio.) [Chemical Formula 76] (hardening compound) E-1: KARAYAD DPHA (manufactured by NIPPON KAYAKU CO., LTD., monomer, molecular weight = 562) E-2: ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD., monomer, molecular weight = 625) E-3: NK ester A-DPH-12E (manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD., monomer, molecular weight = 1107) E-4: NK ester A-TMMT (SHIN-NAKAMURA CHEMICAL CO., LTD) Manufacture, monomer, molecular weight = 352) (photopolymerization initiator) F-1: IRGACURE-OXE01 (manufactured by BASF Corporation) F-2: IRGACURE-OXE02 (manufactured by BASF Corporation) F-3: IRGACURE-369 (BASF) Made by the company) F-4: The following compounds [Chemical Formula 77] (surfactant) W-1: the following mixture (Mw=14000) [Chemical Formula 78] W-2: PolyFox (registered trademark) PF-6320 (manufactured by OMNOVA Solutions Inc.) (solvent) PGMEA: propylene glycol monomethyl ether acetate

（分光特性評價） 以乾燥膜厚成為2μm的方式，將各著色組成物旋轉塗佈在玻璃基板上。 然後，在90℃下，對該塗佈膜進行120秒加熱處理（預烘烤）。 接著，使用i線步進機曝光装置FPA-3000i5+（Canon Inc.製造），以365nm的波長，經由圖案為1.0μm四方的Island圖案遮罩，以200mJ/cm2 的曝光量進行曝光。 接著，在100℃下，對曝光後的塗膜進行300秒加熱處理（後烘烤）。 藉由以上，製造出彩色濾光片。 利用分光光度計MCPD-3000（OTSUKA ELECTRONICS CO.,LTD.製造），對所獲得之彩色濾光片測定透射分光特性。 ＜評價基準＞ 5：波長500nm的透射率小於40%，波長550～650nm的平均透射率小於3%，又，波長400～460nm的最大透射率為85%以上。 4：波長500nm的透射率小於40%，波長550～650nm的平均透射率小於3%，又，波長400～460nm的最大透射率為80%以上且小於85%。 3：波長500nm的透射率小於40%，波長550～650nm的平均透射率小於3%，又，波長400～460nm的最大透射率為75%以上且小於80%。 2：波長500nm的透射率小於40%，波長550～650nm的平均透射率小於3%，又，波長400～460nm的最大透射率為70%以上且小於75%。 1：波長500nm的透射率小於40%，波長550～650nm的平均透射率小於3%，又，波長400～460nm的最大透射率小於70%。 0：波長500nm的透射率為40%以上，或者，波長550～650nm的平均透射率為3%以上。(Evaluation of Spectroscopic Characteristics) Each of the colored compositions was spin-coated on a glass substrate so that the dried film thickness was 2 μm. Then, the coated film was subjected to heat treatment (prebaking) at 90 ° C for 120 seconds. Subsequently, an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used, and the exposure was performed at an exposure amount of 200 mJ/cm 2 through an island pattern mask having a pattern of 1.0 μm square at a wavelength of 365 nm. Next, the exposed coating film was subjected to heat treatment (post-baking) at 100 ° C for 300 seconds. By the above, a color filter is manufactured. The transmission spectroscopic characteristics of the obtained color filter were measured by a spectrophotometer MCPD-3000 (manufactured by OTSUKA ELECTRONICS CO., LTD.). <Evaluation Criteria> 5: The transmittance at a wavelength of 500 nm is less than 40%, the average transmittance at a wavelength of 550 to 650 nm is less than 3%, and the maximum transmittance at a wavelength of 400 to 460 nm is 85% or more. 4: The transmittance at a wavelength of 500 nm is less than 40%, the average transmittance at a wavelength of 550 to 650 nm is less than 3%, and the maximum transmittance at a wavelength of 400 to 460 nm is 80% or more and less than 85%. 3: The transmittance at a wavelength of 500 nm is less than 40%, the average transmittance at a wavelength of 550 to 650 nm is less than 3%, and the maximum transmittance at a wavelength of 400 to 460 nm is 75% or more and less than 80%. 2: The transmittance at a wavelength of 500 nm is less than 40%, the average transmittance at a wavelength of 550 to 650 nm is less than 3%, and the maximum transmittance at a wavelength of 400 to 460 nm is 70% or more and less than 75%. 1: The transmittance at a wavelength of 500 nm is less than 40%, the average transmittance at a wavelength of 550 to 650 nm is less than 3%, and the maximum transmittance at a wavelength of 400 to 460 nm is less than 70%. 0: The transmittance at a wavelength of 500 nm is 40% or more, or the average transmittance at a wavelength of 550 to 650 nm is 3% or more.

（耐溶劑性評價） 以與分光特性評價相同的方法製造出彩色濾光片。將所獲得之彩色濾光片在PGMEA中浸泡10分鐘之後，測定膜厚，計算出殘膜率。 殘膜率=（在PGMEA中浸泡10分鐘之後的彩色濾光片的膜厚/浸泡於PGMEA之前的彩色濾光片的膜厚）×100 ＜評價基準＞ 5：殘膜率為100%。 4：殘膜率為98%以上。 3：殘膜率為95%以上且小於98%。 2：殘膜率為90%以上且小於95%。 1：殘膜率為80%以上且小於90%。 0：殘膜率小於80%。(Evaluation of Solvent Resistance) A color filter was produced in the same manner as the evaluation of the spectral characteristics. After the obtained color filter was immersed in PGMEA for 10 minutes, the film thickness was measured, and the residual film ratio was calculated. Residual film rate = (thickness of color filter after immersion for 10 minutes in PGMEA/film thickness of color filter before immersion in PGMEA) × 100 <Evaluation criteria> 5: Residual film rate was 100%. 4: The residual film ratio is 98% or more. 3: The residual film ratio is 95% or more and less than 98%. 2: The residual film ratio is 90% or more and less than 95%. 1: The residual film ratio is 80% or more and less than 90%. 0: The residual film rate is less than 80%.

（混色評價） 以與分光特性評價相同的方法製造出彩色濾光片。使用MCPD-3000（OTSUKA ELECTRONICS CO.,LTD.製造），對所獲得之彩色濾光片的400～700nm的波長範圍內的最大透射率T0進行測定。 接著，以乾燥後的膜厚成為2μm的方式，將以下所示之混色評價用紅色著色組成物旋轉塗佈於所獲得之彩色濾光片上，在100℃下進行120秒加熱處理（預烘烤）。接著，不進行藉由i線步進機曝光装置之曝光，而是使用四甲基氫氧化銨（TMAH）0.3質量%水溶液，在23℃下進行60秒噴淋式顯影。之後，藉由使用純水之旋轉噴淋法進行沖洗，對混色評價用紅色著色組成物進行顯影去除。 使用MCPD-3000（OTSUKA ELECTRONICS CO.,LTD.製造），對顯影去除混色評價用紅色著色組成物之後的彩色濾光片測定400～700nm的波長範圍內的最大透射率T1。 計算最大透射率變化（ΔT=T0-T1），依據以下基準進行判定。ΔT越小，混色越少，更理想。 ＜評價基準＞ 5：最大透射率變化為0%。 4：最大透射率變化大於0%且小於1%。 3：最大透射率變化為1%以上且小於3%。 2：最大透射率變化為3%以上且小於5%。 1：最大透射率變化為5%以上且小於10%。 0：最大透射率變化為10%以上。 ＜混色評價用紅色著色組成物＞ 藉由珠磨機，將由以下構成之混合液混合、分散15小時，製備出Red顏料分散液。 C.I.顏料紅254　9.9份、 C.I.顏料黃139　4.4份、 顏料衍生物A　1.4份、 含有30質量%分散劑A之PGMEA溶液　15.6份、以及 作為溶劑的PGMEA　41.5份。 接著，均勻地混合如下而製備出混色評價用紅色著色組成物。 上述Red顏料分散液　37.7份、 上述樹脂D-1　5.6份、 上述硬化性化合物 E-1  7份、 光聚合起始劑F-1　3.92份、 上述界面活性劑W-1　0.28份、以及 作為溶劑的PGMEA　51.47份。 ・顏料衍生物A：以下所示之結構 【化學式79】・分散劑A：以下所示之結構 【化學式80】 (Color Mixing Evaluation) A color filter was produced in the same manner as the evaluation of the spectral characteristics. The maximum transmittance T0 in the wavelength range of 400 to 700 nm of the obtained color filter was measured using MCPD-3000 (manufactured by OTSUKA ELECTRONICS CO., LTD.). Then, the red coloring composition for color mixing evaluation shown below was spin-coated on the obtained color filter so that the film thickness after drying became 2 micrometers, and it heat-processed at 100 degreeC for 120 second (pre-bake. grilled). Next, the exposure by the i-line stepper exposure apparatus was not performed, and a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used, and spray development was performed at 23 ° C for 60 seconds. Thereafter, the mixture was washed by a rotary spray method using pure water, and the red coloring composition was subjected to development and removal for color mixing evaluation. Using a MCPD-3000 (manufactured by OTSUKA ELECTRONICS CO., LTD.), the maximum transmittance T1 in the wavelength range of 400 to 700 nm was measured for the color filter after the development of the red coloring composition for color mixing evaluation. The maximum transmittance change (ΔT = T0 - T1) was calculated and judged based on the following criteria. The smaller the ΔT, the less the color mixture is, which is more desirable. <Evaluation Criteria> 5: The maximum transmittance change was 0%. 4: The maximum transmittance change is greater than 0% and less than 1%. 3: The maximum transmittance change is 1% or more and less than 3%. 2: The maximum transmittance change is 3% or more and less than 5%. 1: The maximum transmittance change is 5% or more and less than 10%. 0: The maximum transmittance change is 10% or more. <Red coloring composition for color mixing evaluation> A mixed liquid of the following composition was mixed and dispersed for 15 hours by a bead mill to prepare a red pigment dispersion liquid. CI Pigment Red 254 9.9 parts, CI Pigment Yellow 139 4.4 parts, Pigment Derivative A 1.4 parts, 15.6 parts of PGMEA solution containing 30% by mass of Dispersant A, and 41.5 parts of PGMEA as a solvent. Next, the red coloring composition for color mixing evaluation was prepared by uniformly mixing as follows. 37.7 parts of the red pigment dispersion, 5.6 parts of the above resin D-1, 7 parts of the curable compound E-1, 3.92 parts of the photopolymerization initiator F-1, 0.28 parts of the surfactant W-1, and a solvent 51.47 copies of PGMEA.・Pigment Derivative A: Structure shown below [Chemical Formula 79] ・Dispersant A: The structure shown below [Chemical Formula 80]

（可靠性評價）高溫高濕試験 以與分光評價相同的方法製造出彩色濾光片。在溫度85℃、濕度85%條件下，將所獲得之彩色濾光片放置3天，目視觀察膜面以及用光學顕微鏡觀察膜面。 ＜評價基準＞ 6：如圖1（a）所示，在膜面未確認到分離成分 5：在膜面發現1、2個如圖1（b）所示的微小的分離成分 4：在膜面發現數個如圖1（b）所示的微小的分離成分 3：在膜面發現數十個如圖1（b）所示的微小的分離成分 2：如圖1（c）所示，分離成分呈粒狀出現在膜面上 1：如圖1（d）所示，分離成分呈斑點狀出現在膜面上 0：產生相分離，膜分離為二層 另外，上述中圖1（a）表示圖1的左上框，圖1（b）表示圖1的右上框，圖1（c）表示圖1的左下框，圖1（d）表示圖1的右下框。(Reliability Evaluation) High Temperature and High Humidity Test A color filter was produced in the same manner as the spectroscopic evaluation. The obtained color filter was allowed to stand for 3 days under the conditions of a temperature of 85 ° C and a humidity of 85%, and the film surface was visually observed and the film surface was observed with an optical micro mirror. <Evaluation Criteria> 6: As shown in Fig. 1(a), no separation component 5 was observed on the film surface: 1 or 2 minute separation components 4 as shown in Fig. 1(b) were found on the film surface: on the film surface Several small separation components 3 as shown in Fig. 1(b) were found: dozens of minute separation components 2 as shown in Fig. 1(b) were found on the film surface: as shown in Fig. 1(c), separation The component appears on the surface of the film in a granular form. As shown in Fig. 1(d), the separated component appears as a spot on the surface of the film. 0: phase separation occurs, and the membrane separates into two layers. In addition, the above-mentioned FIG. 1(a) The upper left frame of Fig. 1 is shown, Fig. 1(b) shows the upper right frame of Fig. 1, Fig. 1(c) shows the lower left frame of Fig. 1, and Fig. 1(d) shows the lower right frame of Fig. 1.

【表3】 【表4】 【table 3】 【Table 4】

如上述表所示，實施例的著色組成物能夠製造分光特性良好且耐溶劑性優異之彩色濾光片。又，實施例的彩色濾光片係，與其他顏色之間的混色較小者。又，在高溫高濕試験中，膜成分的分離較小，膜的可靠性亦優異。 另一方面，比較例無法兼顧分光和耐溶劑性。As shown in the above table, the coloring composition of the example can produce a color filter excellent in spectral characteristics and excellent in solvent resistance. Further, the color filter of the embodiment has a smaller color mixture with other colors. Moreover, in the high-temperature and high-humidity test, the separation of the film components is small, and the reliability of the film is also excellent. On the other hand, the comparative example could not achieve both spectral separation and solvent resistance.

無no

圖1係示出可靠性評價的評價基準之圖。FIG. 1 is a diagram showing evaluation criteria of reliability evaluation.

Claims (13)

一種著色組成物，其含有： 具有三芳基甲烷骨架之色素A；具有呫噸骨架之色素B；以及硬化性化合物， 選自前述色素A以及前述色素B之至少一種為色素多聚物。A colored composition comprising: a dye A having a triarylmethane skeleton; a dye B having a xanthene skeleton; and a curable compound selected from at least one of the dye A and the dye B as a dye polymer. 如申請專利範圍第1項所述之著色組成物，其中前述色素A以及前述色素B為色素多聚物。The colored composition according to claim 1, wherein the dye A and the dye B are dye polymers. 如申請專利範圍第1項所述之著色組成物，其中前述色素A的三芳基甲烷骨架的莫耳數與前述色素B的呫噸骨架的莫耳數之比為40:60～75:25。The colored composition according to claim 1, wherein a ratio of a molar number of the triarylmethane skeleton of the dye A to a molar number of the xanthene skeleton of the dye B is 40:60 to 75:25. 如申請專利範圍第1～3項中任一項所述之著色組成物，其中選自前述色素A以及前述色素B之至少一種具有選自雙（磺醯基）亞胺陰離子、三（磺醯基）甲基化物陰離子以及四芳基硼酸鹽陰離子之至少一種陰離子。The colored composition according to any one of claims 1 to 3, wherein at least one selected from the foregoing dye A and the dye B has at least one selected from the group consisting of bis(sulfonyl)imide anion and tris(sulfonate) At least one anion of a methide anion and a tetraarylborate anion. 如申請專利範圍第1～3項中任一項所述之著色組成物，其中前述色素A含有具有三芳基甲烷骨架之陽離子部和經由共價鍵與前述陽離子部鍵結之陰離子。The colored composition according to any one of claims 1 to 3, wherein the dye A contains a cation having a triarylmethane skeleton and an anion bonded to the cation via a covalent bond. 如申請專利範圍第1～3項中任一項所述之著色組成物，其中前述色素B含有具有呫噸骨架之陽離子部和經由共價鍵與前述陽離子部鍵結之陰離子。The coloring composition according to any one of claims 1 to 3, wherein the dye B contains a cation portion having a xanthene skeleton and an anion bonded to the cation portion via a covalent bond. 如申請專利範圍第1～3項中任一項所述之著色組成物，其中選自前述色素A以及前述色素B之至少一種具有含有聚合性不飽和雙鍵之基團。The coloring composition according to any one of the first to third aspects of the present invention, wherein at least one selected from the group consisting of the dye A and the dye B has a group containing a polymerizable unsaturated double bond. 一種彩色濾光片，其使用申請專利範圍第1～7項中任一項所述之著色組成物。A color filter using the coloring composition according to any one of claims 1 to 7. 如申請專利範圍第8項所述之彩色濾光片，其用於有機電致發光元件。A color filter according to claim 8 which is used for an organic electroluminescence element. 一種圖案形成方法，其包括： 使用申請專利範圍第1～7項中任一項所述之著色組成物，在支撐體上形成著色組成物層之製程； 將前述著色組成物層曝光成圖案狀之製程； 對未曝光部進行顯影去除而形成著色圖案之製程；以及 在50～120℃下對前述著色圖案進行加熱之製程。A pattern forming method comprising: a process of forming a colored composition layer on a support by using the colored composition according to any one of claims 1 to 7; and exposing the colored composition layer into a pattern The process of developing a color pattern by developing and removing the unexposed part; and heating the coloring pattern at 50 to 120 ° C. 一種彩色濾光片的製造方法，其包括申請專利範圍第10項所述之圖案形成方法。A method of manufacturing a color filter, comprising the pattern forming method according to claim 10 of the patent application. 一種固體攝像元件，其具有申請專利範圍第8項所述之彩色濾光片。A solid-state imaging device having the color filter of claim 8 of the patent application. 一種圖像顯示装置，其具有申請專利範圍第8項所述之彩色濾光片。An image display device having the color filter of claim 8 of the patent application.
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JP6327173B2 (en) * 2014-02-27 2018-05-23 Jsr株式会社 Colored composition, colored cured film, and display element

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